U.S. patent application number 13/323179 was filed with the patent office on 2012-06-28 for actinic-ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the same.
This patent application is currently assigned to FUJIFILM Corporation. Invention is credited to Yusuke Iizuka, Shohei Kataoka, Akinori Shibuya, Naohiro Tango, Shuhei Yamaguchi.
Application Number | 20120164573 13/323179 |
Document ID | / |
Family ID | 46317630 |
Filed Date | 2012-06-28 |
United States Patent
Application |
20120164573 |
Kind Code |
A1 |
Tango; Naohiro ; et
al. |
June 28, 2012 |
ACTINIC-RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION, AND
RESIST FILM AND PATTERN FORMING METHOD USING THE SAME
Abstract
An actinic-ray-sensitive or radiation-sensitive resin
composition capable of forming a pattern having excellent critical
dimension uniformity (CDU) in the line width, and a pattern forming
method using the same are provided. The actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention
includes (A) a resin containing a repeating unit having a specific
lactone structure and a repeating unit having a specific monocyclic
alicyclic structure, which increases a solubility in an alkaline
developer by the action of an acid, and (B) a compound having a
specific structure, which generates an acid upon irradiation with
an actinic-ray or a radiation.
Inventors: |
Tango; Naohiro; (Shizuoka,
JP) ; Iizuka; Yusuke; (Shizuoka, JP) ;
Shibuya; Akinori; (Shizuoka, JP) ; Yamaguchi;
Shuhei; (Shizuoka, JP) ; Kataoka; Shohei;
(Shizuoka, JP) |
Assignee: |
FUJIFILM Corporation
Tokyo
JP
|
Family ID: |
46317630 |
Appl. No.: |
13/323179 |
Filed: |
December 12, 2011 |
Current U.S.
Class: |
430/281.1 ;
430/325 |
Current CPC
Class: |
G03F 7/0045 20130101;
G03F 7/0046 20130101; G03F 7/0397 20130101; G03F 7/2041
20130101 |
Class at
Publication: |
430/281.1 ;
430/325 |
International
Class: |
G03F 7/20 20060101
G03F007/20; G03F 7/027 20060101 G03F007/027 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 27, 2010 |
JP |
2010-291380 |
Claims
1. An actinic-ray-sensitive or radiation-sensitive resin
composition comprising: (A) a resin containing a repeating unit
represented by the following general formula (A-I) and a repeating
unit represented by the following general formula (1), which
increases a solubility in an alkaline developer by the action of an
acid, and (B) a compound represented by the following general
formula (ZI-3), which generates an acid upon irradiation with an
actinic-ray or a radiation. ##STR00183## (In the general formula
(A-I), R.sub.01 represents a hydrogen atom or an alkyl group)
##STR00184## (In the general formula (1), R.sub.1 represents a
hydrogen atom or an alkyl group, R.sub.2 represents an alkyl group
or a cycloalkyl group, and R represents an atomic group required
for forming a monocyclic alicyclic structure in cooperation with a
carbon atom) ##STR00185## (In the general formula (ZI-3), each of
R.sub.1c to R.sub.5c independently represents a hydrogen atom, an
alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an
aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group,
a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a
nitro group, an alkylthio group, or an arylthio group, each of
R.sub.6c and R.sub.7c independently represents a hydrogen atom, an
alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or
an aryl group, each of R.sub.x and R.sub.y independently represents
an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a
2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group
or vinyl group, any two or more of R.sub.1c to R.sub.5c, R.sub.5c
and R.sub.6c, R.sub.6c, and R.sub.7c, R.sub.5c and R.sub.x, and
R.sub.x and R.sub.y may be bonded to each other to form a ring
structure, and the ring structure may contain an oxygen atom, a
sulfur atom, a ketone group, an ester bond, or an amide bond, and
Z.sup.- represents a sulfonate anion).
2. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 1, further comprising a hydrophobic
resin (C).
3. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 1, further comprising a
low-molecular-weight compound (D) containing a nitrogen atom and
containing a group which is cleaved by the action of an acid.
4. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 1, further comprising a compound
which generates an acid upon irradiation with an actinic-ray or a
radiation, which is different from the compound represented by the
general formula (ZI-3).
5. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 1, wherein the repeating unit
represented by the general formula (1) is a repeating unit
represented by the following general formula (1-1). ##STR00186##
(In the general formula (I-1), R.sub.1 represents a hydrogen atom
or an alkyl group, and R.sub.2 represents an alkyl group or a
cycloalkyl group)
6. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 1, wherein the resin which increases
a solubility in an alkaline developer by the action of an acid
further contains a repeating unit having an alicyclic hydrocarbon
structure substituted with a hydroxyl group.
7. A resist film formed using the actinic-ray-sensitive or
radiation-sensitive resin composition according to claim 1.
8. A pattern forming method comprising: exposing the resist film
according to claim 7, and developing the exposed resist film.
9. The pattern forming method according to claim 8, wherein the
exposure is liquid immersion exposure.
10. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 2, further comprising a
low-molecular-weight compound (D) containing a nitrogen atom and
containing a group which is cleaved by the action of an acid.
11. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 2, further comprising a compound
which generates an acid upon irradiation with an actinic-ray or a
radiation, which is different from the compound represented by the
general formula (ZI-3).
12. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 3, further comprising a compound
which generates an acid upon irradiation with an actinic-ray or a
radiation, which is different from the compound represented by the
general formula (ZI-3).
13. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 2, wherein the repeating unit
represented by the general formula (1) is a repeating unit
represented by the following general formula (1-1). ##STR00187##
(In the general formula (1-1), R.sub.1 and R.sub.2 are the same as
R.sub.1 and R.sub.2 above)
14. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 3, wherein the repeating unit
represented by the general formula (1) is a repeating unit
represented by the following general formula (1-1). ##STR00188##
(In the general formula (1-1), R.sub.1 and R.sub.2 are the same as
R.sub.1 and R.sub.2 above)
15. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 4, wherein the repeating unit
represented by the general formula (1) is a repeating unit
represented by the following general formula (1-1). ##STR00189##
(In the general formula (1-1), R.sub.1 and R.sub.2 are the same as
R.sub.1 and R.sub.2 above)
16. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 2, wherein the resin which increases
a solubility in an alkaline developer by the action of an acid
further contains a repeating unit having an alicyclic hydrocarbon
structure substituted with a hydroxyl group.
17. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 3, wherein the resin which increases
a solubility in an alkaline developer by the action of an acid
further contains a repeating unit having an alicyclic hydrocarbon
structure substituted with a hydroxyl group.
18. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 4, wherein the resin which increases
a solubility in an alkaline developer by the action of an acid
further contains a repeating unit having an alicyclic hydrocarbon
structure substituted with a hydroxyl group.
19. The actinic-ray-sensitive or radiation-sensitive resin
composition according to claim 5, wherein the resin which increases
a solubility in an alkaline developer by the action of an acid
further contains a repeating unit having an alicyclic hydrocarbon
structure substituted with a hydroxyl group.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an actinic-ray-sensitive or
radiation-sensitive resin composition, and a resist film and a
pattern forming method using the same. More specifically, the
present invention relates to an actinic-ray-sensitive or
radiation-sensitive resin composition applicable to a production
process of a semiconductor such as IC, a production process of a
circuit board for a liquid crystal, a thermal head, or the like,
and other lithography processes of photofabrication, and a resist
film and a pattern forming method using the same. Particularly, the
present invention relates to an actinic-ray-sensitive or
radiation-sensitive resin composition which is suitable when far
ultraviolet radioactive rays at a wavelength of 250 nm or less, an
electron beam, or the like is used as an irradiation source, and a
resist film and a pattern forming method using the same.
[0003] 2. Description of the Related Art
[0004] A chemical amplification type resist composition is a
material for pattern formation, which generates an acid in the
exposed areas upon irradiation with radiation such as far
ultraviolet rays and the like, and undergoes a reaction catalyzed
by this acid, and as a result, comes to have a variance in the
solubility in a developer between the areas irradiated with the
actinic radioactive ray and the unirradiated areas, thereby forming
a pattern on the substrate.
[0005] In the case where a KrF excimer laser is employed as an
exposure light source, a resin having a poly(hydroxystyrene)
skeleton which shows reduced absorption mainly in a 248-nm region,
is used as the main component in the chemical amplification resist
composition. Consequently, the composition has high sensitivity and
high resolution, and forms a good pattern, and it is hence a better
system, as compared with a conventional
naphthoquinonediazide/novolak resin system.
[0006] On the other hand, in the case where a light source having a
shorter wavelength, for example, an ArF excimer laser (193 nm), is
employed as an exposure light source, compounds having aromatic
groups used in the chemical amplification resist composition
intrinsically show considerable absorption in a 193-nm region, and
thus, this composition cannot be said to be a favorable system.
[0007] Consequently, resist compositions for an ArF excimer laser,
which contain a resin with an alicyclic hydrocarbon structure, have
been developed.
[0008] Furthermore, in accordance with the miniaturization of
semiconductor elements, the wavelength shortening of the exposure
light source and the realization of high numerical apertures (high
NA) for projector lenses have been advanced. In this regard, a high
resolving power due to the wavelength shortening has been required.
As one of the methods for realizing a high resolving power, it is
heretofore known to employ a so-called liquid immersion technique,
that is, a method in which the space between a projector lens and a
sample is filled with a liquid with a high refractive index
(hereinafter also referred to as a "liquid for liquid immersion").
The liquid immersion method is effective for any of pattern shapes
at present, and can be combined with a super-resolution technology
such as a phase shift method, a modified illumination method, and
the like now under study.
[0009] A resist composition for an ArF excimer laser (193 nm) using
such the chemical amplification mechanism is mainly used at
present. However, in case of a fine pattern having a line width of
110 nm or less is formed, the resist composition has been required
to be further improved from the viewpoint of the comprehensive
performances.
[0010] From the viewpoint of improvement of the comprehensive
performances as the resist composition, resist compositions
including repeating units having various lactone structures are
known (see, for example, JP2008-257198A, JP2005-31624A,
JP2010-159393A, JP2006-18229A, JP2009-86445A, JP2005-234330A, and
JP2005-234119A).
[0011] However, even with the use of a resist composition including
repeating units having various lactone structures, critical
dimension uniformity (CDU) in the line width of a pattern which is
one of the comprehensive performances as a resist has been required
to be further improved. In particular, when forming a fine pattern
having a line width of 110 nm or less, there are demands for a
resist composition having excellent CDU.
SUMMARY OF THE INVENTION
[0012] An object of the present invention to provide an
actinic-ray-sensitive or radiation-sensitive resin composition
capable of forming a pattern having excellent critical dimension
uniformity (CDU) in the line width, and a resist film and a pattern
forming method using the same.
[0013] An actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention obtained by solving the
above-described problems is characterized in that it includes (A) a
resin which increases a solubility in an alkaline developer by the
action of an acid, including a repeating unit represented by the
following general formula (A-I) and a repeating unit represented by
the following general formula (1), and (B) a compound represented
by the following general formula (ZI-3), which generates an acid
upon irradiation with an actinic-ray or a radiation.
##STR00001## [0014] In the general formula (A-I), [0015] R.sub.01
represents a hydrogen atom or an alkyl group.
[0015] ##STR00002## [0016] In the general formula (1), [0017]
R.sub.1 represents a hydrogen atom or an alkyl group, [0018]
R.sub.2 represents an alkyl group or a cycloalkyl group, and [0019]
R represents an atomic group required for forming a monocyclic
alicyclic structure in cooperation with a carbon atom.
[0019] ##STR00003## [0020] In the general formula (ZI-3), [0021]
each of R.sub.1c to R.sub.5c independently represents a hydrogen
atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy
group, an aryloxy group, an alkoxycarbonyl group, an
alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen
atom, a hydroxyl group, a nitro group, an alkylthio group, or an
arylthio group, [0022] each of R.sub.6c, and R.sub.7c independently
represents a hydrogen atom, an alkyl group, a cycloalkyl group, a
halogen atom, a cyano group, or an aryl group, [0023] each of
R.sub.x and R.sub.y independently represents an alkyl group, a
cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an
alkoxycarbonylalkyl group, an allyl group, or a vinyl group, [0024]
at least any two or more of R.sub.1c to R.sub.5c, R.sub.5c and
R.sub.6c, R.sub.6c and R.sub.7c, R.sub.5c and R.sub.x, and R.sub.x
and R.sub.y may be bonded to each other to form a ring structure,
and this ring structure may contain an oxygen atom, a sulfur atom,
a ketone group, an ester bond, or an amide bond, and [0025] Z.sup.-
represents a sulfonate anion.
[0026] It is a preferable embodiment of the composition of the
present invention that the composition further includes a
hydrophobic resin (C), a low-molecular-weight compound (D) having a
group which is cleaved by the action of an acid, and further
includes, which is different from the compound represented by the
general formula (ZI-3), a compound which generates an acid upon
irradiation with an actinic-ray or a radiation.
[0027] It is another preferable embodiment of the composition of
the present invention that the repeating unit represented by the
general formula (I) is a repeating unit represented by the
following general formula (1-1).
##STR00004## [0028] In the general formula (1-1), [0029] R.sub.1
represents a hydrogen atom or an alkyl group, and [0030] R.sub.2
represents an alkyl group or a cycloalkyl group.
[0031] It is still another preferable embodiment of the composition
of the present invention that the resin (A) further has a repeating
unit having an alicyclic hydrocarbon structure substituted with a
hydroxyl group.
[0032] The present invention further includes a resist film formed
using the actinic-ray-sensitive or radiation-sensitive resin
composition.
[0033] The present invention still further includes a pattern
forming method including exposing the above-described resist film
and developing the exposed resist film.
[0034] It is another preferable embodiment of the pattern forming
method of the present invention that the exposure is a liquid
immersion exposure.
[0035] The present invention preferably has the following
configuration.
[0036] That is, in the composition of the present invention, the
sulfonate anion Z.sup.- in the general formula (ZI-3) is
represented by the following general formula (III).
##STR00005## [0037] In the general formula (III), [0038] each
R.sub.p independently represents an alkyl group, a cycloalkyl
group, or an aryl group, [0039] L represents a single bond or a
linking group, and [0040] p1 represents an integer of 1 to 8, and
p2 represents 1 or 2.
[0041] In the case where p2 is 2, two R.sub.p's may be the same as
or different from each other and two R.sub.p's may be bonded to
each other to form a ring structure.
[0042] Furthermore, besides the compound represented by the general
formula (ZI-3), the compound which generates an acid upon
irradiation with an actinic-ray or a radiation is a
triarylsulfonium compound.
[0043] Furthermore, the low-molecular-weight compound (D)
containing a nitrogen atom and containing a group which is cleaved
by the action of an acid preferably has a structure represented by
the following general formula (A).
##STR00006## [0044] In the general formula (A), Ra represents a
hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group,
or an aralkyl group. Further, with n=2, two Ra's may be the same as
or different from each other, or the two Ra's may be bonded to each
other to form a divalent heterocyclic hydrocarbon group or a
derivative thereof.
[0045] Rb represents a hydrogen atom, an alkyl group, a cycloalkyl
group, an aryl group, an aralkyl group, or an alkoxyalkyl group.
However, in --C(Rb)(Rb)(Rb), when one or more Rb's are hydrogen
atoms, at least one of the remaining Rb's is a cyclopropyl group, a
1-alkoxyalkyl group, or an aryl group.
[0046] Two Rb's may be bonded to each other to form an alicyclic
hydrocarbon group, aromatic hydrocarbon group, a heterocyclic
hydrocarbon group, or a derivative thereof.
[0047] n represents an integer of 0 to 2, and m represents an
integer of 1 to 3, with n+m=3
[0048] In the pattern forming method of the present invention, the
exposure is preferably an exposure by an ArF excimer laser.
[0049] According to the present invention, it is possible to
provide an actinic-ray-sensitive or radiation-sensitive resin
composition capable of forming a pattern having excellent critical
dimension uniformity (CDU) in the line width, and a resist film and
a pattern forming method using the same.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0050] Preferable embodiments of the present invention are
described in detail below.
[0051] Incidentally, a group or atomic group as denoted herein
without specifying whether substituted or unsubstituted includes
both a group having no substituent and a group having a
substituent. For example, the "alkyl group" includes, when whether
substituted or unsubstituted is unspecified, not only an alkyl
group having no substituent (unsubstituted alkyl group) but also an
alkyl group having a substituent (substituted alkyl group).
[0052] Furthermore, the "actinic-ray" or the "radiation" in the
present specification mean, for example, bright line spectra from a
mercury lamp, far ultraviolet radioactive rays typically such as an
excimer laser, extreme ultraviolet rays (EUV radiation), X-rays, an
electron beam (EB), or the like. Further, the "light" as used in
the present invention means an actinic-ray or a radiation.
[0053] In addition, the "exposure" in the present specification
includes not only light irradiation with a mercury lamp, far
ultraviolet radioactive rays typically such as an excimer laser,
X-rays, EUV radiation, or the like but also the lithography by
means of particle beams such as an electron beam, an ion beam, and
the like, unless otherwise specified.
[0054] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention includes: [0055] (A) a resin
which increases a solubility in an alkaline developer by the action
of an acid, including a repeating unit represented by the following
general formula (A-I) and a repeating unit represented by the
following general formula (1), and [0056] (B) a compound
represented by the following general formula (ZI-3), which
generates an acid upon irradiation with an actinic-ray or a
radiation.
[0056] ##STR00007## [0057] In the general formula (A-I), [0058]
R.sub.01 represents a hydrogen atom or an alkyl group.
[0058] ##STR00008## [0059] In the general formula (I), [0060]
R.sub.1 represents a hydrogen atom or an alkyl group, [0061]
R.sub.2 represents an alkyl group or a cycloalkyl group, and [0062]
R represents an atomic group required for forming a monocyclic
alicyclic structure in cooperation with a carbon atom.
[0062] ##STR00009## [0063] In the general formula (ZI-3), [0064]
each of R.sub.1c to R.sub.5c independently represents a hydrogen
atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy
group, an aryloxy group, an alkoxycarbonyl group, an
alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen
atom, a hydroxyl group, a nitro group, an alkylthio group, or an
arylthio group, [0065] each of R.sub.6c and R.sub.7c independently
represents a hydrogen atom, an alkyl group, a cycloalkyl group, a
halogen atom, a cyano group, or an aryl group, [0066] each of
R.sub.x and R.sub.y independently represents an alkyl group, a
cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an
alkoxycarbonylalkyl group, an allyl group or vinyl group, [0067] at
least any two or more of R.sub.1c to R.sub.5c, R.sub.5c and
R.sub.6c, R.sub.6c and R.sub.7c, R.sub.5c and R.sub.x, and R.sub.x
and R.sub.y may be bonded to each other to form a ring structure,
and this ring structure may contain an oxygen atom, a sulfur atom,
a ketone group, an ester bond, or an amide bond, and [0068] Z.sup.-
represents a sulfonate anion.
[0069] [1] (A) Resin which increases a solubility in an alkaline
developer by the action of an acid, including a repeating unit
represented by the following general formula (A-I) and a repeating
unit represented by the following general formula (1) (which is
also simply referred to as a "resin (A)")
[0070] In the present invention, the resin (A) has a repeating unit
represented by the following general formula (A-I).
##STR00010## [0071] In the general formula (A-I), [0072] R.sub.01
represents a hydrogen atom or an alkyl group.
[0073] The alkyl group of R.sub.01 is preferably an alkyl group
having 1 to 4 carbon atoms, more preferably a methyl group or an
ethyl group, and particularly preferably a methyl group. The alkyl
group in R.sub.01 may be substituted, and examples of the
substituent include a halogen atom such as a fluorine atom, a
chlorine atom, a bromine atom, and the like; a mercapto group; a
hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy
group, an isopropoxy group, a t-butoxy group, a benzyloxy group,
and the like; and an acyloxy group such as an acetyloxy group, a
propionyloxy group, and the like. R.sub.01 is preferably a hydrogen
atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl
group, more preferably a hydrogen atom or a methyl group, and still
more preferably a methyl group.
[0074] The repeating unit represented by the general formula (A-I)
group is generally present in the form of optical isomers. Any of
the optical isomers may be used. It is both appropriate to use a
single type of optical isomer alone and to use a plurality of
optical isomers in the form of a mixture. When a single type of
optical isomer is mainly used, the optical purity (ee) thereof is
preferably 90% or more, and more preferably 95% or more.
[0075] The content of the repeating unit represented by the general
formula (A-I), the sum thereof when a plurality of repeating units
are contained, is preferably in the range of 15 to 70 mol %, more
preferably 20 to 65 mol %, and most preferably 30 to 60 mol %,
based on all the repeating units in the resin (A).
[0076] In the present invention, the resin (A) further has a
repeating unit represented by the following general formula
(1).
##STR00011## [0077] In the general formula (1), [0078] R.sub.1
represents a hydrogen atom or an alkyl group, [0079] R.sub.2
represents an alkyl group or a cycloalkyl group, and [0080] R
represents an atomic group required for forming a monocyclic
alicyclic structure in cooperation with a carbon atom.
[0081] The repeating unit represented by the general formula (1)
may correspond to a repeating unit which decomposes by the action
of an acid to cause an alkali-soluble group (which is also referred
to as an "acid-decomposable group").
[0082] Specific examples and preferable examples of the alkyl group
with respect to R.sub.1 include the specific examples and the
preferable examples of R.sub.01 of the general formula (A-I).
R.sub.1 preferably a represents a hydrogen atom, a methyl group, a
trifluoromethyl group, or a hydroxymethyl group.
[0083] The alkyl group in R.sub.2 may be linear or branched, and
may have a substituent. Examples of the alkyl group in R.sub.2
include a methyl group, an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, an isobutyl group, a t-butyl
group, and the like.
[0084] The cycloalkyl group in R.sub.2 may be monocyclic or
polycyclic, and may have a substituent. Examples of the cycloalkyl
group in R.sub.2 include a monocyclic cycloalkyl group such as a
cyclopentyl group, a cyclohexyl group, and the like.
[0085] R.sub.2 is preferably an alkyl group, more preferably one
having 1 to 10 carbon atoms, and still more preferably one having 1
to 5 carbon atoms, and examples thereof include a methyl group and
an ethyl group.
[0086] R represents an atomic group required for forming an
alicyclic structure in cooperation with a carbon atom. The
alicyclic structure formed by cooperation of R with a carbon atom
is a monocyclic alicyclic structure (for example, a cyclopentyl
group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl
group), and the number of carbon atoms is preferably 3 to 8, more
preferably 3 to 7, and most preferably 5 or 6.
[0087] Furthermore, the repeating unit represented by the general
formula (1) is preferably a repeating unit represented by the
following general formula (1-1).
##STR00012## [0088] In the general formula (1-1), R.sub.1 and
R.sub.2 have the same meanings as in the general formula (1).
[0089] The repeating unit represented by the general formula (1)
may be used singly or in combination of two or more kinds
thereof.
[0090] The content of the repeating unit represented by the general
formula (1) (the sum thereof when a plurality of repeating units
are contained), is preferably in the range of 15 to 70 mol %, more
preferably 20 to 65 mol %, and most preferably 30 to 65 mol %,
based on all the repeating units in the resin (A).
[0091] The repeating unit represented by the general formula (1)
can be used in combination with other repeating units having an
acid-decomposable group.
[0092] Examples of such other repeating units having an
acid-decomposable group that can be used in combination include
those in which the group corresponding to R.sub.2 in the general
formula (1) is a methyl group or an ethyl group, and the a ring
formed by R is an adamantane ring.
[0093] In the present invention, in one embodiment in which other
repeating units having an acid-decomposable group are used in
combination, the repeating units in which a group corresponding to
R.sub.2 in the general formula (1-1) is a methyl group or an ethyl
group, and the repeating units in which a group corresponding to
R.sub.2 in the general formula (1) is a methyl group or an ethyl
group, and the a ring formed by R is an adamantane ring, are
preferably used in combination with each other.
[0094] In the case where other repeating unit having an
acid-decomposable group is used in addition to the repeating unit
represented by the general formula (1), the total content of the
repeating unit represented by the general formula (1) and other
repeating units having an acid-decomposable group is preferably 15
to 70 mol %, more preferably 20 to 65 mol %, and most preferably 30
to 65 mol %, based on all the repeating units in the resin (A).
[0095] It is preferable for the resin (A) to have a repeating unit
having a hydroxyl group or a cyano group. The possession of this
repeating unit realizes enhancements of adhesion of a resist film
to a substrate, and developer affinity. The repeating unit having a
hydroxyl group or a cyano group is preferably a repeating unit with
a structure of an alicyclic hydrocarbon substituted with a hydroxyl
group or a cyano group. In the alicyclic hydrocarbon structure
substituted with a hydroxyl group or a cyano group, the alicyclic
hydrocarbon structure preferably consists of an adamantyl group, a
diamantyl group, or a norbornyl group. Preferable examples of the
alicyclic hydrocarbon structures substituted with a hydroxyl group
or a cyano group include a monohydroxyadamantyl group, a
dihydroxyadamantyl group, a monohydroxydiamantyl group, a
dihydroxydiamantyl group, a cyano group-substituted norbornyl
group, and the like.
[0096] Examples of the repeating unit having the atomic group
include repeating units represented by the following general
formulae (AIIa) to (AIId).
##STR00013## [0097] In the general formulae (AIIa) to (AIId),
[0098] R.sub.1c represents a hydrogen atom, a methyl group, a
trifluoromethyl group, or hydroxymethyl group, and [0099] each of
R.sub.2c to R.sub.4c independently represents a hydrogen atom, a
hydroxyl group, or cyano group, provided that at least one of
R.sub.2c to R.sub.4c represents a hydroxyl group or cyano group.
Preferably, one or two of R.sub.2c to R.sub.4c are hydroxyl groups,
and the rest are hydrogen atoms. In the general formula (VIIa),
more preferably, two of R.sub.2c to R.sub.4c are hydroxyl groups,
and the reset are hydrogen atoms.
[0100] The content of the repeating unit having a hydroxyl group or
a cyano group is preferably 5 to 40 mol %, more preferably 5 to 30
mol %, and most preferably 10 to 25 mol %, based on all the
repeating units in the resin (A).
[0101] Specific examples of the repeating unit having a hydroxyl
group or a cyano group will be shown below, but the present
invention is not limited thereto.
##STR00014## ##STR00015##
[0102] The resin used in the actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention may
include a repeating unit having an alkali-soluble group. Examples
of the alkali-soluble group include a carboxyl group, a sulfonamido
group, a sulfonylimido group, a bissulfonylimido group, and an
aliphatic alcohol substituted at its .alpha.-position with an
electron-withdrawing group (for example, a hexafluoroisopropanol
group). The possession of a repeating unit having a carboxyl group
is more preferred. The possession of the repeating unit having an
alkali-soluble group increases the resolving power in contact hole
usage.
[0103] The repeating unit having an alkali-soluble group is
preferably any of a repeating unit wherein the alkali-soluble group
is directly bonded to the main chain of a resin such as a repeating
unit of acrylic acid or methacrylic acid, a repeating unit wherein
the alkali-soluble group is bonded via a linking group to the main
chain of a resin and a repeating unit wherein the alkali-soluble
group is introduced in a terminal of a polymer chain by the use of
a chain transfer agent or polymerization initiator having the
alkali-soluble group in the stage of polymerization. The linking
group may have a monocyclic or polycyclic cyclohydrocarbon
structure. The repeating unit of an acrylic acid or a methacrylic
acid is particularly preferred.
[0104] The resin (A) in the present invention may not contain a
repeating unit having an alkali-soluble group, but in the case
where it contains a repeating unit having an alkali-soluble group,
the content of the repeating unit having an alkali-soluble group is
preferably from 1 to 20 mol %, more preferably from 3 to 15 mol %,
and most preferably from 5 to 10 mol %, based on all the repeating
units of the resin (A).
[0105] Specific examples of the repeating units having an
alkali-soluble group will be shown below, but the present invention
is not limited thereto.
[0106] In the specific examples, Rx represents H, CH.sub.3,
CH.sub.2OH, or CF.sub.3.
##STR00016##
[0107] The resin (A) in the present invention can further contain a
repeating unit that has a structure of an alicyclic hydrocarbon
structure having no polar group (for example, the alkali-soluble
group, the hydroxyl group, and the cyano group as described above),
exhibiting no acid decomposability. Examples of such a repeating
unit include a repeating unit represented by the general formula
(IV) below.
##STR00017##
[0108] In the general formula (IV), R.sub.5 represents a
hydrocarbon group having at least one cyclic structure and having
no polar group.
[0109] Ra represents a hydrogen atom, an alkyl group, or a
--CH.sub.2--O--Ra.sub.2 group, in which Ra.sub.2 represents a
hydrogen atom, an alkyl group, or an acyl group. Ra preferably
represents a hydrogen atom, a methyl group, a hydroxymethyl group,
or a trifluoromethyl group, and particularly preferably a hydrogen
atom or a methyl group.
[0110] The cyclic structures contained in R.sub.5 include a
monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
Examples of the monocyclic hydrocarbon group include a cycloalkyl
group having 3 to 12 carbon atoms, such as a cyclopentyl group, a
cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the
like, or a cycloalkenyl group having 3 to 12 carbon atoms, such as
a cyclohexenyl group and the like. Examples of the monocyclic
hydrocarbon group preferably include a monocyclic hydrocarbon group
having 3 to 7 carbon atoms, and more preferably a cyclopentyl group
and a cyclohexyl group.
[0111] Examples of the polycyclic hydrocarbon group include a
ring-assembly hydrocarbon group and a crosslinked-ring hydrocarbon
group. Examples of the ring-assembly hydrocarbon group include a
bicyclohexyl group, a perhydronaphthalene group, and the like.
Examples of the crosslinked-ring hydrocarbon ring include a
bicyclic hydrocarbon ring, such as a pinane ring, a bornane ring, a
norpinane ring, a norbornane ring, a bicyclooctane ring (for
example, a bicyclo[2.2.2]octane ring, a bicyclo[3.2.1]octane ring,
and the like), etc.; a tricyclic hydrocarbon ring such as a
homopaddlane ring, an adamantane ring, a
tricyclo[5.2.1.0.sup.2,6]decane ring, a
tricyclo[4.3.1.1.sup.2,5]undecane ring, and the like; and a
tetracyclic hydrocarbon ring such as a
tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodecane ring a
perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like.
Further, the crosslinked-ring hydrocarbon rings include a
condensed-ring hydrocarbon ring, for example, condensed rings
formed by condensation of a plurality of 5- to 8-membered
cycloalkane rings, such as a perhydronaphthalene (decalin) ring, a
perhydroanthracene ring, a perhydrophenanthrene ring, a
perhydroacenaphthene ring, a perhydrofluorene ring, a
perhydroindene ring, a perhydrophenarene ring, and the like.
[0112] Examples of the preferable crosslinked-ring hydrocarbon ring
include a norbornyl group, an adamantyl group, a bicyclooctanyl
group, a tricyclo[5,2,1,0.sup.2,6]decanyl group, and the like.
Examples of the more preferable crosslinked-ring hydrocarbon ring
include a norbornyl group and an adamantyl group.
[0113] Such an alicyclic hydrocarbon group may have a substituent,
and preferable examples of the substituents include a halogen atom,
an alkyl group, a hydroxyl group substituted with a hydrogen atom,
an amino group substituted with a hydrogen atom, and the like.
Preferable examples of the halogen atom include a bromine atom, a
chlorine atom, and a fluorine atom, and preferable examples of the
alkyl group include a methyl group, an ethyl group, a butyl group,
and a t-butyl group. The alkyl group may further have a
substituent, and examples of the substituent include a halogen
atom, an alkyl group, a hydroxyl group substituted with a hydrogen
atom, and an amino group substituted with a hydrogen atom.
[0114] Examples of the substituent of the hydrogen atom include an
alkyl group, a cycloalkyl group, an aralkyl group, a substituted
methyl group, a substituted ethyl group, an alkoxycarbonyl group,
and an aralkyloxycarbonyl group. Preferable examples of the alkyl
group include an alkyl group having 1 to 4 carbon atoms, preferable
examples of the substituted methyl group include a methoxymethyl
group, a methoxythiomethyl, group a benzyloxymethyl group, a
t-butoxymethyl group, and a 2-methoxyethoxymethyl group, and
preferable examples of the substituted ethyl group include a
1-ethoxyethyl group and a 1-methyl-1-methoxyethyl group. Preferable
examples of the acyl group include an aliphatic acyl group having 1
to 6 carbon atoms, such as a formyl group, an acetyl group, a
propionyl group, a butyryl group, an isobutyryl group, a valeryl
group, a pivaloyl group, and the like. Examples of the
alkoxycarbonyl group include an alkoxycarbonyl group having 1 to 4
carbon atoms, and the like.
[0115] The resin (A) may or may not contain the repeating units
that have a structure of an alicyclic hydrocarbon having no polar
group and exhibiting no acid decomposability, but in the case where
the resin (A) may contain such repeating units, the content of the
repeating units is preferably from 1 to 40 mol %, and more
preferably from 2 to 20 mol %, based on all the repeating units of
resin (B).
[0116] Specific examples of the repeating units that have a
structure of an alicyclic hydrocarbon having no polar group, and
exhibiting no acid decomposability will be shown below, but the
present invention is not limited thereto. In the formulae, Ra
represents H, CH.sub.3, CH.sub.2OH, or CF.sub.3.
##STR00018## ##STR00019##
[0117] The Resin (A) used in the actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention may
have, in addition to the above-described repeating structural
units, various repeating structural units for the purpose of
regulating the dry etching resistance, standard developer
adaptability, substrate adhesion, resist profile and generally
required properties of the resist such as resolving power, heat
resistance, sensitivity, and the like.
[0118] Examples of such a repeating structural unit include the
repeating structural units corresponding to the following monomers,
which however are nonlimiting.
[0119] The use of such repeating structural units would enable fine
regulation of the required properties of the resin used in the
actinic-ray-sensitive or radiation-sensitive resin composition of
the present invention, in particularly, (1) solubility in applied
solvents, (2) film forming easiness (glass transition point), (3)
alkali developability, (4) film thinning (selection of
hydrophilicity/hydrophobicity and alkali-soluble groups), (5)
adhesion of unexposed area to a substrate, (6) dry etching
resistance, and the like.
[0120] Examples of such a monomer include a compound having an
unsaturated bond, capable of addition polymerization, which is
selected from acrylic esters, methacrylic esters, acrylamides,
methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and
the like; etc.
[0121] In addition, any unsaturated compound capable of addition
polymerization that is copolymerizable with monomers corresponding
to the above various repeating structural units may be
copolymerized therewith.
[0122] The molar ratios of the respective repeating structural
units in the resin (A) used in the actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention are
appropriately determined from the viewpoint of regulation of not
only the dry etching resistance of the resist but also the standard
developer adaptability, substrate adhesion, resist profile, and
generally required performances of the resist, such as the
resolution power, heat resistance, sensitivity, and the like. It is
ensured that the content of the respective repeating structural
units is no more than 100 mol % in total.
[0123] When the actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention is one for ArF exposure, it is
preferable for the resin (A) used in the actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention to
have substantially no aromatic group from the viewpoint of
transparency to an ArF beam. More specifically, the proportion of
the repeating units having an aromatic group is preferably 5 mol %
or less, more preferably 3 mol % or less, or ideally 0 mol %, that
is, the repeating unit having an aromatic group is not contained,
in total in all the repeating units of the resin (A). Further, the
resin (A) preferably has a monocyclic or polycyclic alicyclic
hydrocarbon structure.
[0124] Further, from the viewpoint of the compatibility with the
hydrophobic resin (C) as described later, it is preferable for the
resin (A) to contain neither a fluorine atom nor a silicon
atom.
[0125] Further, in the resin (A) used in the actinic-ray-sensitive
or radiation-sensitive resin composition of the present invention,
preferably, all the repeating units consist of (meth)acrylate-based
repeating units. In this case, use can be made of any of resins
(A), wherein all the repeating units consist of methacrylate-based
repeating units, wherein all the repeating units consist of
acrylate-based repeating units, and wherein all the repeating units
consist of methacrylate-based repeating units and acrylate-based
repeating units. However, it is preferable for the acrylate-based
repeating units to account for 50 mol % or less of all the
repeating units.
[0126] The resin (A) in the present invention may be a commercially
available product, if available, but can be synthesized by
conventional techniques (for example, radical polymerization).
Examples of the general synthetic methods include a batch
polymerization method in which a monomer species and an initiator
are dissolved in a solvent and heated so as to accomplish
polymerization, a dropping polymerization method in which a
solution of monomer species and initiator is added by dropping to a
heated solvent over 1 to 10 hours, and the like, with the dropping
polymerization method being preferred. Examples of the reaction
solvent include ethers such as tetrahydrofuran, 1,4-dioxane,
diisopropyl ether, and the like; ketones such as methyl ethyl
ketone, methyl isobutyl ketone, and the like; ester solvents such
as ethyl acetate; amide solvents such as dimethylformamide,
dimethylacetamide, and the like; solvents capable of dissolving the
actinic-ray-sensitive or radiation-sensitive resin composition,
such as propylene glycol monomethyl ether acetate, propylene glycol
monomethyl ether, and cyclohexanone, as described hereinafter. It
is preferable to perform the polymerization with the use of the
same solvent as employed in the actinic-ray-sensitive or
radiation-sensitive resin composition, whereby any particle
generation during storage can be inhibited.
[0127] The polymerization reaction is preferably carried out in an
atmosphere of inert gas, such as nitrogen or argon. The
polymerization is initiated by the use of a commercially available
radical initiator (an azo-based initiator, peroxide, and the like)
as a polymerization initiator. As the radical initiators, an
azo-based initiator is preferable. An azo-based initiator having an
ester group, a cyano group or a carboxyl group is particularly
preferable. Preferable examples of the initiators include
azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl
2,2'-azobis(2-methylpropionate), and the like. According to
necessity, the initiator is added additionally or in separate
portions, and after completion of the reaction, the initiator is
put into a solvent and a polymer is collected, for example, in the
powder or solid form. The concentration during the reaction is from
5 to 50% by mass, and preferably from 10 to 30% by mass. The
reaction temperature is generally from 10.degree. C. to 150.degree.
C., preferably from 30.degree. C. to 120.degree. C., and more
preferably from 60.degree. C. to 100.degree. C.
[0128] In addition, in order to inhibit aggregation of the resin
after preparation of the composition, or the like, a step in which
a resin synthesized is dissolved in a solvent to give a solution,
and the solution is heated at about 30.degree. C. to 90.degree. C.
for approximately 30 minutes to 4 hours, as described in, for
example, JP2009-037108A.
[0129] The weight average molecular weight of the resin (A) of the
present invention is preferably 1,000 to 200,000, more preferably
2,000 to 20,000, still more preferably 3,000 to 15,000, and
particularly preferably 3,000 to 12,000 in terms of a polystyrene
standard as measured by means of GPC. The regulation of the weight
average molecular weight to 1,000 to 200,000 increases the
viscosity of the composition, to prevent deterioration of
film-forming property. Further, deterioration of heat resistance
and dry etching resistance, as well as deterioration of
developability can be prevented by using the composition of the
present invention.
[0130] Use is made of the resin (A) whose dispersity (molecular
weight distribution) is generally from 1.0 to 3.0, preferably from
1.0 to 2.6, more preferably from 1.0 to 2.0, and most 1.4 to 2.0.
The lower the molecular weight distribution, the more excellent the
resolving power and resist profile, and the smoother the side wall
of the resist pattern to thereby attain an excellence in
roughness.
[0131] In the present invention, the content ratio of resin (A)
based on the total solid content of the whole composition is
preferably from 30 to 99% by mass, and more preferably from 60 to
95% by mass.
[0132] Furthermore, the resin (A) of the present invention may be
used singly or in combination of two or more kinds thereof.
[0133] [2] (B) Compound Represented by Following General Formula
(ZI-3), Which Generates Acid upon Irradiation with Actinic-ray or
radiation.
[0134] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention includes a compound which
generates an acid upon irradiation with an actinic-ray or a
radiation (which is also referred to as an "acid generator"), which
is a compound represented by the following general formula (ZI-3)
(which is also referred to as a "compound (ZI-3)").
[0135] The compound (ZI-3) in the present invention is a compound
having a phenacylsulfonium structure.
##STR00020## [0136] In the general formula (ZI-3), [0137] each of
R.sub.1c to R.sub.5c independently represents a hydrogen atom, an
alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an
aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group,
a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a
nitro group, an alkylthio group, or an arylthio group, [0138] each
of R.sub.6c and R.sub.7c independently represents a hydrogen atom,
an alkyl group, a cycloalkyl group, a halogen atom, a cyano group,
or an aryl group, [0139] each of R.sub.x and R.sub.y independently
represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group,
a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl
group or vinyl group, and [0140] any two or more of R.sub.1c to
R.sub.5c, R.sub.5c and R.sub.6c, R.sub.6c and R.sub.7c, R.sub.5c
and R.sub.x, and R.sub.c and R.sub.y may be bonded to each other to
form a ring structure, and this ring structure may contain an
oxygen atom, a sulfur atom, a ketone group, an ester bond, or an
amide bond.
[0141] The ring structure includes an aromatic or non-aromatic
hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring,
and a polycyclic condensed ring formed by combination of two or
more of these rings. The ring structure includes a 3- to
10-membered ring, and is preferably a 4- to 8-membered ring, and
more preferably a 5- or 6-membered ring.
[0142] Examples of the group formed by bonding of any two or more
of R.sub.1c to R.sub.5c, R.sub.6c and R.sub.7c, and R.sub.x and
R.sub.y include a butylene group, a pentylene group, and the
like.
[0143] The group formed by bonding of R.sub.5c and R.sub.6c, and
R.sub.5c and R.sub.x is preferably a single bond or an alkylene
group, and examples of the alkylene group include a methylene
group, an ethylene group, and the like.
[0144] Z.sup.- represents a sulfonate anion.
[0145] The alkyl group as R.sub.1c to R.sub.7c may be either linear
or branched, and examples thereof include an alkyl group having 1
to 20 carbon atoms, and preferably a linear or branched alkyl group
having 1 to 12 carbon atoms (for example, a methyl group, an ethyl
group, a linear or branched propyl group, a linear or branched
butyl group, and a linear or branched pentyl group), and examples
of the cycloalkyl group include a cycloalkyl group having 3 to 8
carbon atoms (for example, a cyclopentyl group and a cyclohexyl
group).
[0146] The aryl group as R.sub.1c to R.sub.7c preferably has 5 to
15 carbon atoms, and examples thereof include a phenyl group and a
naphthyl group.
[0147] The alkoxy group as R.sub.1c to R.sub.5c may be any of
linear, branched, and cyclic, and examples thereof include an
alkoxy group having 1 to 10 carbon atoms, preferably a linear and
branched alkoxy group having 1 to 5 carbon atoms (for example, a
methoxy group, an ethoxy group, a linear or branched propoxy group,
a linear or branched butoxy group, and a linear or branched pentoxy
group), and cyclic alkoxy group having 3 to 8 carbon atoms (for
example, a cyclopentyloxy group and a cyclohexyloxy group).
[0148] Specific examples of the alkoxy group in the alkoxycarbonyl
group as R.sub.1c to R.sub.5c include the same as those of the
alkoxy group as R.sub.1c to R.sub.5c.
[0149] Specific examples of the alkyl group in the alkylcarbonyloxy
group and the alkylthio group as R.sub.1c to R.sub.5c include the
same as those of the alkyl group as R.sub.1c to R.sub.5c.
[0150] Specific examples of the aryl group in the aryloxy group and
the arylthio group as R.sub.1c to R.sub.5c include the same as
those of the aryl group as R.sub.1c to R.sub.5c.
[0151] Preferably, any one of R.sub.1c to R.sub.5c is a linear or
branched alkyl group, a cycloalkyl group, or a linear, branched, or
cyclic alkoxy group, and R.sub.1c to R.sub.5c more preferably has 2
to 15 carbon atoms, due to which the solvent solubility is more
enhanced and production of particles during storage is be
suppressed.
[0152] The ring structure formed by bonding of any two or more of
R.sub.1c to R.sub.5c preferably includes a 5- or 6-membered ring,
and particularly preferably a 6-membered ring (such as a phenyl
ring).
[0153] The ring structure formed by the mutual bonding of R.sub.5c
and R.sub.6c preferably includes a 4 or greater-membered ring
(preferably a 5- or 6-membered ring) formed with the carbonyl
carbon atom and carbon atom in the general formula (I) by the
mutual bonding of R.sub.5c and R.sub.6c to constitute a single bond
or an alkylene group (a methylene group, an ethylene group, and the
like).
[0154] The aryl group as any of R.sub.6c and R.sub.7c is an alkyl
group having 5 to 15 carbon atoms, and examples thereof include a
phenyl group and a naphthyl group.
[0155] Furthermore, in the case where R.sub.6c and R.sub.7c are
combined to form a ring, the group formed by bonding of R.sub.6c
and R.sub.7c is preferably an alkylene group having 2 to 10 carbon
atoms, and examples thereof include an ethylene group, a propylene
group, a butylene group, a pentylene group, a hexylene group, and
the like. Further, the ring formed by bonding of R.sub.6c and
R.sub.7c may contain a heteroatom such as an oxygen atom and the
like in the ring.
[0156] Examples of the alkyl group and the cycloalkyl group as
R.sub.x and R.sub.y include the same as those of the alkyl group
and the cycloalkyl group as in R.sub.1c to R.sub.7c.
[0157] Examples of the 2-oxoalkyl group and the 2-oxocycloalkyl
group as R.sub.x and R.sub.y include a group containing >C.dbd.O
at the 2-position of the alkyl group and the cycloalkyl group as
R.sub.1c to R.sub.7c.
[0158] Examples of the alkoxy group in the alkoxycarbonylalkyl
group as R.sub.x and R.sub.y are the same as those of the alkoxy
group in R.sub.1c to R.sub.5c. Examples of the alkyl group include
an alkyl group having 1 to 12 carbon atoms, and preferably a linear
alkyl group having 1 to 5 carbon atoms (for example, a methyl group
and an ethyl group).
[0159] The allyl group as R.sub.x and R.sub.y is not particularly
limited but is preferably an unsubstituted allyl group or an allyl
group substituted with a monocyclic or polycyclic cycloalkyl group
(preferably a cycloalkyl group having 3 to 10 carbon atoms).
[0160] The vinyl group as R.sub.x and R.sub.y is not particularly
limited but is preferably an unsubstituted vinyl group or a vinyl
group substituted with a monocyclic or polycyclic cycloalkyl group
(preferably a cycloalkyl group having 3 to 10 carbon atoms).
[0161] The ring structure which may be formed by the mutual bonding
of R.sub.x and R.sub.y include a 5- or 6-membered ring, and
preferably a 5-membered ring (that is, a tetraydrothiophene ring),
formed together with the sulfur atom in the general formula (ZI-3)
by divalent R.sub.x and R.sub.y (for example, a methylene group, an
ethylene group, a propylene group, and the like).
[0162] R.sub.x and R.sub.y are each preferably an alkyl group, or a
cycloalkyl group having 4 or more carbon atoms, more preferably an
alkyl group, or a cycloalkyl group having 6 or more carbon atoms,
and still more preferably an alkyl group, or a cycloalkyl group
having 8 or more carbon atoms.
[0163] R.sub.1c to R.sub.7c, R.sub.x and R.sub.y may further
contain a substituent, and examples of such a substituent include a
halogen atom (for example, a fluorine atom), a hydroxyl group, a
carboxyl group, a cyano group, a nitro group, an alkyl group, a
cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group,
an acyl group, an arylcarbonyl group, an alkoxyalkyl group, an
aryloxyalkyl group, an alkoxycarbonyl group, an aryloxycarbonyl
group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and
the like.
[0164] Examples of the alkyl group include a linear or branched
alkyl group having 1 to 12 carbon atoms, such as a methyl group, an
ethyl group, an n-propyl group, an i-propyl group, an n-butyl
group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl
group, and the like.
[0165] Examples of the cycloalkyl group include a cycloalkyl group
having 3 to 10 carbon atoms, such as a cyclopentyl group, a
cyclohexyl group, and the like.
[0166] Examples of the aryl group include an aryl group having 6 to
15 carbon atoms, such as a phenyl group, a naphthyl group, and the
like.
[0167] Examples of the alkoxy group include a linear, branched, or
cyclic alkoxy group having 1 to 20 carbon atoms, such as a methoxy
group, an ethoxy group, an n-propoxy group, an i-propoxy group, an
n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a
t-butoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and
the like.
[0168] Examples of the aryloxy group include an aryloxy group
having 6 to 10 carbon atoms, such as a phenyloxy group, a
naphthyloxy group, and the like.
[0169] Examples of the acyl group include a linear or branched acyl
group having 2 to 12 carbon atoms, such as an acetyl group, a
propionyl group, an n-butanoyl group, an i-butanoyl group, an
n-heptanoyl group, a 2-methylbutanoyl group, a 1-methylbutanoyl
group, a t-heptanoyl group, and the like.
[0170] Examples of the arylcarbonyl group include an aryloxy group
having 6 to 10 carbon atoms, such as a phenylcarbonyl group, a
naphthylcarbonyl group, and the like.
[0171] Examples of the alkoxyalkyl group include a linear,
branched, or cyclic alkoxyalkyl group having 2 to 21 carbon atoms,
such as a methoxymethyl group, an ethoxymethyl group, a
1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl
group, a 2-ethoxyethyl group, and the like.
[0172] Examples of the aryloxyalkyl group include an aryloxy group
having 7 to 12 carbon atoms, such as a phenyloxymethyl group,
phenyloxyethyl group, a naphthyloxymethyl group, a naphthyloxyethyl
group, and the like.
[0173] Examples of the alkoxycarbonyl group include a linear,
branched, or cyclic alkoxycarbonyl group having 2 to 21 carbon
atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an
n-propoxycarbonyl group, an i-propoxycarbonyl group, an
n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, a
1-methylpropoxycarbonyl group, a t-butoxycarbonyl group, a
cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl, and the
like.
[0174] Examples of the aryloxycarbonyl group include an
aryloxycarbonyl group having 7 to 11 carbon atoms, such as a
phenyloxycarbonyl group, a naphthyloxycarbonyl group, and the
like.
[0175] Examples of the alkoxycarbonyloxy group include a linear,
branched, or cyclic alkoxycarbonyloxy group having 2 to 21 carbon
atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy
group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy
group, an n-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, a
cyclopentyloxycarbonyloxy group, a cyclohexyloxycarbonyloxy, and
the like.
[0176] Examples of the aryloxycarbonyloxy group include an
aryloxycarbonyloxy group having 7 to 11 carbon atoms, such as a
phenyloxycarbonyloxy group, a naphthyloxycarbonyloxy group, and the
like.
[0177] In the general formula (ZI-3), it is more preferable that
each of R.sub.1c, R.sub.2c, R.sub.4c, and R.sub.5c independently
represent a hydrogen atom, and R.sub.3c represent a group except
for a hydrogen atom, that is, represent an alkyl group, a
cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group,
an alkoxycarbonyl group, an alkylcarbonyloxy group, a
cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a
nitro group, an alkylthio group, or an arylthio group.
[0178] Z.sup.- represents a sulfonate anion as a non-nucleophilic
anion.
[0179] The non-nucleophilic anion is an anion having an exceedingly
low ability of causing a nucleophilic reaction, and is also an
anion capable of suppressing the decomposition over time by the
nucleophilic reaction in the molecule, which thus leads to
improvement of the stability over time of the resist.
[0180] Examples of the sulfonate anion include an aliphatic
sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate
anion, and the like.
[0181] The aliphatic moiety in the aliphatic sulfonate anion may be
an alkyl group or a cycloalkyl group, and preferable examples
thereof include an alkyl group having 1 to 30 carbon atoms and a
cycloalkyl group having 3 to 30 carbon atoms, for example, a methyl
group, an ethyl group, a propyl group, an isopropyl group, an
n-butyl group, an isobutyl group, a sec-butyl group, a pentyl
group, a neopentyl group, a hexyl group, a heptyl group, an octyl
group, a nonyl group, a decyl group, an undecyl group, a dodecyl
group, a tridecyl group, a tetradecyl group, a pentadecyl group, a
hexadecyl group, a heptadecyl group, an octadecyl group, a
nonadecyl group, an eicosyl group, a cyclopropyl group, a
cyclopentyl group, a cyclohexyl group, an adamantyl group, a
norbornyl group, a bornyl group, and the like.
[0182] Preferable examples of the aromatic group in the aromatic
sulfonate anion and the aromatic carboxylate anion include an aryl
group preferably having 6 to 14 carbon atoms, such as a phenyl
group, a tolyl group, a naphthyl group, and the like.
[0183] The alkyl group, the cycloalkyl group, and the aryl group of
the aliphatic sulfonate anion and the aromatic sulfonate anion may
have a substituent. Examples of the substituent of the alkyl group,
the cycloalkyl group, and the aryl group of the aliphatic sulfonate
anion and the aromatic sulfonate anion include a nitro group, a
halogen atom such as a fluorine atom and the like, a carboxyl
group, a hydroxyl group, an amino group, a cyano group, an alkoxy
group (preferably having 1 to 15 carbon atoms), an a cycloalkyl
group (preferably having 3 to 15 carbon atoms), an aryl group
(preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group
(preferably having 2 to 7 carbon atoms), an acyl group (preferably
having 2 to 12 carbon atoms), an alkoxycarbonyloxy group
(preferably having 2 to 7 carbon atoms), an alkylthio group
(preferably having 1 to 15 carbon atoms), an alkylsulfonyl group
(preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl
group (preferably having 2 to 15 carbon atoms), an aryloxysulfonyl
group (preferably having 6 to 20 carbon atoms), an
alkylaryloxysulfonyl group (preferably having 7 to 20 carbon
atoms), an a cycloalkylaryloxysulfonyl group (preferably having 10
to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5
to 20 carbon atoms), an a cycloalkylalkyloxyalkyloxy group
(preferably having 8 to 20 carbon atoms), and the like. The aryl
group or the ring structure which may be further contained in these
groups has an alkyl group (preferably having 1 to 15 carbon atoms)
as its substituent.
[0184] The non-nucleophilic anion of Z.sup.- is preferably an
aliphatic sulfonate anion substituted at its .alpha.-position of
sulfonic acid with a fluorine atom, or an aromatic sulfonate anion
substituted with a fluorine atom or a group having a fluorine atom.
The non-nucleophilic anion is more preferably a perfluoroaliphatic
sulfonate anion having 4 to 8 carbon atoms, and still more
preferably a nonafluorobutane sulfonate anion, a perfluorooctane
sulfonate anion, a pentafluorobenzene sulfonate anion, or a
3,5-bis(trifluoromethyl)benzene sulfonate anion.
[0185] Specific examples of the cation moiety of the compound
(ZI-3) will be shown below.
##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##
##STR00026## ##STR00027##
[0186] The sulfonate anion for Z.sup.- is particularly preferably
represented by the following general formula (III) from the
viewpoint of the sensitivity.
##STR00028## [0187] In the general formula (III), [0188] in the
case where a plurality of R.sub.p's are present, each of them
independently represents an alkyl group, a cycloalkyl group, or an
aryl group.
[0189] L represents a single bond or a linking group.
[0190] p1 represents an integer of 1 to 8, and p2 represents 1 or
2.
[0191] In the case where p2 is 2, two R.sub.p's may be the same as
or different from each other and two R.sub.p's may be bonded to
each other to form a ring structure.
[0192] Specific examples of the alkyl group, the cycloalkyl group,
and the aryl group represented by R.sub.p include a chained alkyl
group, a monocyclic alkyl group, a polycyclic hydrocarbon group,
and a monocyclic aryl group, and the chained alkyl group, the
monocyclic alkyl group, the polycyclic hydrocarbon group, or the
monocyclic aryl group may have a substituent. The substituent may
have a fluorine atom.
[0193] The chained alkyl group may be linear or branch chained, and
examples thereof include methyl, ethyl, propyl, butyl, pentyl,
hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl,
t-butyl, iso-amyl, and the like.
[0194] The alkyl group may have a substituent, and examples of the
substituent include a hydroxyl group, a halogen atom (fluorine,
chlorine, bromine, and iodine), a nitro group, a cyano group, an
amido group, a sulfonamido group, an alkyl group (a methyl group,
an ethyl group, a propyl group, an n-butyl group, a sec-butyl
group, a hexyl group, a 2-ethylhexyl group, an octyl group, and the
like), an alkoxy group (a methoxy group, an ethoxy group, a
hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, a
butoxy group, and the like), an alkoxycarbonyl group (a
methoxycarbonyl group, an ethoxycarbonyl group, and the like), an
acyl group (a formyl group, an acetyl group, a benzoyl group, and
the like), an acyloxy group (an acetoxy group, a butyryloxy group,
and the like), and a carboxy group.
[0195] Examples of the monocyclic alkyl group include cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, and
the like, and particularly preferably cyclopropyl, cyclopentyl,
cyclohexyl, and cyclooctyl.
[0196] The monocyclic alkyl group may have a substituent, and
examples of the substituent include a halogen atom (fluorine,
chlorine, bromine, and iodine), a nitro group, a cyano group, an
amido group, a sulfonamido group, a methyl group, an alkyl group
(an ethyl group, a propyl group, an n-butyl group, a sec-butyl
group, a hexyl group, a 2-ethylhexyl group, an octyl group, and the
like), an alkoxy group (a methoxy group, an ethoxy group, a
hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, a
butoxy group, and the like), an alkoxycarbonyl group (a
methoxycarbonyl group, an ethoxycarbonyl group, and the like), an
acyl group (a formyl group, an acetyl group, a benzoyl group, and
the like), an acyloxy group (an acetoxy group, a butyryloxy group,
and the like), and a carboxy group.
[0197] Examples of the polycyclic hydrocarbon group include
bicyclo[4.3.0]nonanyl, decahydronaphthalenyl,
tricyclo[5.2.1.0(2,6)]decanyl, bornyl, isobornyl, norbornyl,
adamantyl, noradamantyl,
1,7,7-trimethyltricyclo[2.2.1.0.sup.2,6]heptanyl,
3,7,7-trimethylbicyclo[4.1.0]heptanyl, and the like, and
particularly preferably norbornyl, adamantyl, and noradamantyl.
[0198] The monocyclic aryl group means a substituted or substituted
phenyl group, and examples of the substituent include a hydroxyl
group, a halogen atom (fluorine, chlorine, bromine, and iodine), a
nitro group, a cyano group, an amido group, a sulfonamido group, an
alkyl group (a methyl group, an ethyl group, a propyl group, an
n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl
group, an octyl group, and the like), an alkoxy group (a methoxy
group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a
hydroxypropoxy group, a butoxy group, and the like), an
alkoxycarbonyl group (a methoxycarbonyl group, an ethoxycarbonyl
group, and the like), an acyl group (a formyl group, an acetyl
group, a benzoyl group, and the like), an acyloxy group (an acetoxy
group, a butyryloxy group, and the like), and a carboxy group.
[0199] Further, R.sub.p preferably has no fluorine atom from the
viewpoint of a low fluorine content.
[0200] Examples of the linking group for L include a divalent
linking group when p2 is 1, and a trivalent linking group when p2
is 2.
[0201] Examples of the divalent linking group for L include an
oxygen atom (--O--), a sulfur atom (--S--), a nitrogen atom
(--NH--), a carboxyl group (--OC.dbd.O--, --CO(.dbd.O)--), an amido
group (--NHC(.dbd.O)--), a sulfonamido group (--NHSO.sub.2--), and
the like.
[0202] Examples of the trivalent linking group for L include a
nitrogen atom (>N--), an amido group (>NC(.dbd.O)--), a
sulfonamido group (>NSO.sub.2--), and the like. Particularly, in
the case where p2 is 2 and two R.sub.p's are bonded to each other
to form a ring, L is preferably a nitrogen atom-containing linking
group such as an amido group, a sulfonamido group, and the like.
Here, two R.sub.p's may be bonded to each other to form a cyclic
amine residue having a nitrogen atom on L in the ring.
[0203] Examples of the cyclic amine residue structure include
aziridine, azetidine, pyrrolidine, piperidine, hexamethyleneimine,
heptamethyleneimine, piperazine, decahydroquinoline,
8-azabicyclo[3.2.1]octane, indole, oxazolidine, thiazolidine,
2-azanorbornane, 7-azanorbornane, morpholine, thiamorpholine, and
the like. The groups may have a substituent. Examples of the
substituent include a hydroxyl group, a halogen atom (fluorine,
chlorine, bromine, and iodine), a nitro group, a cyano group, an
amido group, a sulfonamido group, an alkyl group (a methyl group,
an ethyl group, a propyl group, an n-butyl group, a sec-butyl
group, a hexyl group, a 2-ethylhexyl group, an octyl group, and the
like), an alkoxy group (a methoxy group, an ethoxy group, a
hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, a
butoxy group, and the like), an alkoxycarbonyl group (a
methoxycarbonyl group, an ethoxycarbonyl group, and the like), an
acyl group (a formyl group, an acetyl group, a benzoyl group, a
carbonyl group on carbon as a constituent of a ring, and the like),
an acyloxy group (acetoxy group, butyryloxy group, and the like),
and a carboxy group.
[0204] As for the sulfonate anion represented by the general
formula (III), it is a preferable embodiment that R.sub.p is a
cycloalkyl group or an aryl group, or that when p2 is 2, two
R.sub.p's are bonded to each other to form a ring.
[0205] Examples of the sulfonate anion as Z.sup.- include specific
examples below.
##STR00029## ##STR00030## ##STR00031##
[0206] Specific examples of the compound (ZI-3) will be shown
below, but the present invention is not limited thereto.
##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##
##STR00037## ##STR00038## ##STR00039## ##STR00040##
##STR00041##
[0207] The compound (ZI-3) is used singly or in combination of two
or more kinds thereof.
[0208] The compound (ZI-3) can be prepared in accordance with any
method, for example, the method described in [0157] of
JP2002-236359A, the method described in [0316] of JP2004-139014A,
or the like. Particularly, the sulfonate anion represented by the
general formula (III) can be prepared in accordance with the method
described in, for example, [0362] to [0372] of JP2005-266766A.
[0209] The content of the compound (ZI-3) is preferably 3 to 30% by
mass, more preferably 7 to 30% by mass, and still more preferably 7
to 25% by mass, based on all the solids of the composition.
[0210] Furthermore, the compound (ZI-3) in the present invention
may also be used in combination with an acid generator (which is
also referred to as an acid generator to be used with the other
components), which is different form the compound (ZI-3).
[0211] The acid generator to be used with the other components is
not particularly limited, but preferable examples thereof include
compounds represented by the following general formulae (ZI'),
(ZII'), and (ZIII').
##STR00042## [0212] In the general formula (ZI'), each of
R.sub.201, R.sub.202, and R.sub.203 represents an organic
group.
[0213] The number of carbon atoms of the organic group as any of
R.sub.201, R.sub.202, and R.sub.203 is generally 1 to 30, and
preferably 1 to 20.
[0214] Furthermore, two of R.sub.201 to R.sub.203 may be bonded to
form a ring structure, and an oxygen atom, a sulfur atom, an ester
bond, an amide bond, or a carbonyl group may be contained in the
ring. Examples of the ring formed by the mutual bonding of two of
R.sub.201 to R.sub.203 include an alkylene group (for example, a
butylene group and a pentylene group).
[0215] Z.sup.- represents a non-nucleophilic anion (anion having an
exceedingly low ability of causing a nucleophilic reaction).
[0216] Examples of Z.sup.- include a sulfonate anion (an aliphatic
sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate
anion, and the like), a carboxylate anion (an aliphatic carboxylate
anion, an aromatic carboxylate anion, an aralkyl carboxylate anion,
and the like), a sulfonylimide anion, a bis(alkylsulfonyl)imide
anion, a tris(alkylsulfonyl)methide anion, and the like.
[0217] Specific examples and preferable examples of the sulfonate
anion include the same as those of the sulfonate anion described
above with respect to the sulfonate anion in the general formula
(ZI-3).
[0218] Examples of the aliphatic moiety in the aliphatic
carboxylate anion include the same as those in the sulfonate anion
described above with respect to the sulfonate anion in the general
formula (ZI-3).
[0219] Examples of the aromatic moiety in the aromatic carboxylate
anion include the same as those in the sulfonate anion described
above with respect to the sulfonate anion in the general formula
(ZI-3).
[0220] Preferable examples of the aralkyl group in the
aralkylcarboxylate anion include an aralkyl group having 6 to 12
carbon atoms, such as a benzyl group, a phenethyl group, a
naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group,
and the like.
[0221] Examples of the sulfonylimide anion include a saccharin
anion. The alkyl group of the bis(alkylsulfonyl)imido anion and the
tris(alkylsulfonyl)methyl anion is preferably an alkyl group having
1 to 5 carbon atoms. Examples of the substituent of the alkyl group
include a halogen atom, an alkyl group substituted with a halogen
atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl
group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group,
and the like, with a fluorine atom or an alkyl group substituted
with a fluorine atom being preferred.
[0222] Examples of the other Z.sup.- include phosphorus fluoride
(for example, PF.sub.6.sup.-), boron fluoride (for example,
BF.sub.4.sup.-), antimony fluoride (for example, SbF.sub.6.sup.-),
and the like.
[0223] Z.sup.- is preferably an aliphatic sulfonate anion
substituted at its .alpha.-position of sulfonic acid with a
fluorine atom, an aromatic sulfonate anion substituted with a
fluorine atom or a group having a fluorine atom, a
bis(alkylsulfonyl)imido anion whose alkyl group is substituted with
a fluorine atom, or a tris(alkylsulfonyl)methide anion whose alkyl
group is substituted with a fluorine atom. The nonnucleophilic
anion is more preferably a perfluorinated aliphatic sulfonate anion
(more preferably having 4 to 8 carbon atoms) or a benzene sulfonate
anion having a fluorine atom, and still more preferably a
nonafluorobutane sulfonate anion, a perfluorooctane sulfonate
anion, a pentafluorobenzene sulfonate anion, or a
3,5-bis(trifluoromethyl)benzene sulfonate anion.
[0224] From the viewpoint of acid strength, the pKa of the acid
generated is preferably -1 or less in order to improve the
sensitivity.
[0225] Examples of the organic groups represented by R.sub.201,
R.sub.202, and R.sub.203 include groups corresponding to the
following compounds (ZI'-1) and (ZI'-2) as described later.
[0226] Further, a compound having a plurality of the structures of
the general formula (ZI') may be used. For example, a compound may
have a structure wherein at least one of R.sub.201 to R.sub.203 of
the compound of the general formula (ZI') is bonded with at least
one of R.sub.201 to R.sub.203 of another compound of the general
formula (ZI') via a single bond or a linking group.
[0227] More preferable examples of the (ZI') component include the
following compounds (ZI'-1) and (ZI'-2).
[0228] The compound (ZI'-1) is the arylsulfonium compound of the
general formula (ZI') wherein at least one of R.sub.201 to
R.sub.203 is an aryl group, that is, a compound containing an
arylsulfonium as a cation.
[0229] In the arylsulfonium compounds, all of R.sub.201 to
R.sub.203 may be aryl groups, or R.sub.201 to R.sub.203 may be
partially aryl groups and the remainder thereof may be alkyl groups
or cycloalkyl groups, but it is preferable that all of R.sub.201 to
R.sub.203 be aryl groups.
[0230] Examples of the arylsulfonium compound include a
triarylsulfonium compound, a diarylalkylsulfonium compound, an
aryldialkylsulfonium compound, a diarylcycloalkylsulfonium
compound, and an aryldicycloalkylsulfonium compound, with the
triarylsulfonium compound being preferred.
[0231] The aryl group of the arylsulfonium compound is preferably a
phenyl group or a naphthyl group, and more preferably a phenyl
group. The aryl group may be an aryl group having a heterocyclic
structure, containing an oxygen atom, a nitrogen atom, a sulfur
atom, or the like. Examples of the heterocyclic structure include a
pyrrole residue, a furan residue, a thiophene residue, an indole
residue, a benzofuran residue, a benzothiophene residue, and the
like. In the case where the arylsulfonium compound has two or more
aryl groups, the two or more aryl groups may be the same as or
different from each other.
[0232] The alkyl group, or a cycloalkyl group which the
arylsulfonium compound may have, if necessary, is preferably a
linear or branched alkyl group having 1 to 15 carbon atoms or a
cycloalkyl group having 3 to 15 carbon atoms, and examples thereof
include a methyl group, an ethyl group, a propyl group, an n-butyl
group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a
cyclobutyl group, a cyclohexyl group, and the like.
[0233] The aryl group, the alkyl group, or the cycloalkyl group of
R.sub.201 to R.sub.203 may have an alkyl group (for example, having
1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to
15 carbon atoms), an aryl group (for example, having 6 to 14 carbon
atoms), an alkoxy group (for example, having 1 to 15 carbon atoms),
a halogen atom, a hydroxyl group, or a phenylthio group as a
substituent. Examples of the preferable substituent include a
linear or branched alkyl group having 1 to 12 carbon atoms, a
cycloalkyl group having 3 to 12 carbon atoms, and a linear,
branched, or cyclic alkoxy group having 1 to 12 carbon atoms, and
more preferably an alkyl group having 1 to 4 carbon atoms and an
alkoxy group having 1 to 4 carbon atoms. The substituent may be
substituted with any one of the three groups, R.sub.201 to
R.sub.203, or may be substituted with all of the three groups.
Further, in the case where R.sub.201 to R.sub.203 are aryl groups,
the substituent is preferably substituted at the p-position of the
aryl group.
[0234] Next, the compound (ZI'-2) will be described.
[0235] The compound (ZI'-2) is a compound in which each of
R.sub.201 to R.sub.203 in the formula (ZI') independently
represents an organic group having no aromatic ring. Here, the
aromatic ring also includes an aromatic ring containing a
heteroatom.
[0236] The organic group containing no aromatic ring as R.sub.201
to R.sub.203 generally contains 1 to 30 carbon atoms, and
preferably 1 to 20 carbon atoms.
[0237] R.sub.201 to R.sub.203 each independently preferably
represent an alkyl group, a cycloalkyl group, an allyl group, or a
vinyl group, still more preferably a linear or branched 2-oxoalkyl
group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group,
and particularly preferably a linear or branched 2-oxoalkyl
group.
[0238] Preferable examples of the alkyl group and the cycloalkyl
group of R.sub.201 to R.sub.203 include a linear or branched alkyl
group having 1 to 10 carbon atoms (for example, a methyl group, an
ethyl group, a propyl group, a butyl group, and a pentyl group),
and a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl
group, a cyclohexyl group, and a norbornyl group). More preferable
examples of the alkyl group include a 2-oxoalkyl group and an
alkoxycarbonylmethyl group, and more preferable examples of the
cycloalkyl group include a 2-oxocycloalkyl group.
[0239] The 2-oxoalkyl group may be either linear or branched, and
examples thereof include a group containing >C.dbd.O at the
2-position of the alkyl group.
[0240] The 2-oxocycloalkyl group is preferably the group containing
>C.dbd.O at the 2-position of the cycloalkyl group.
[0241] Examples of the alkoxy group in the alkoxycarbonylmethyl
group preferably include an alkoxy group having 1 to 5 carbon atoms
(a methoxy group, an ethoxy group, a propoxy group, a butoxy group,
and a pentoxy group).
[0242] R.sub.201 to R.sub.203 may be further substituted with a
halogen atom, an alkoxyl group (for example, having 1 to 5 carbon
atoms), a hydroxyl group, a cyano group, or a nitro group.
[0243] Next the general formulae (ZII') and (ZIII') will be
described.
[0244] In the general formulae (ZII') and (ZIII'), [0245] each of
R.sub.204 to R.sub.207 independently represents an aryl group, an
alkyl group, or a cycloalkyl group.
[0246] The aryl group, the alkyl group, and the cycloalkyl group of
R.sub.204 to R.sub.207 are the same as the aryl group described as
the aryl group, the alkyl group, and the cycloalkyl group of
R.sub.201 to R.sub.203 of the compound (ZI'-1) as described
above.
[0247] The aryl group, the alkyl group, and the cycloalkyl group of
R.sub.204 to R.sub.207 may have a substituent. Examples of the
substituent include those which may be contained in the aryl group,
the alkyl group, and the cycloalkyl group of R.sub.201 to R.sub.203
of the compound (ZI'-1).
[0248] Z.sup.- represents a non-nucleophilic anion, and examples
thereof include the same as those in Z.sup.- in the general formula
(ZI').
[0249] Further examples of the acid generator to be used with the
other components, which can be used in combination with the
compound (ZI-3) in the present invention include compounds
represented by the following general formulae (ZIV'), (ZV'), and
(ZVI').
##STR00043## [0250] In the general formulae (ZIV') to (ZVI'),
[0251] each of Ar.sub.3 and Ar.sub.4 independently represents an
aryl group, [0252] each of R.sub.208, R.sub.209, and R.sub.210
independently represents an alkyl group, a cycloalkyl group, or an
aryl group, and [0253] A represents an alkylene group, an
alkenylene group, or an arylene group.
[0254] Specific examples of the aryl group of Ar.sub.3, Ar.sub.4,
R.sub.208, R.sub.209, and R.sub.210 include the same as those of
the aryl group as R.sub.201, R.sub.202, and R.sub.203 in the
general formula (ZI'-1).
[0255] Specific examples of the alkyl group and the cycloalkyl
group of R.sub.208, R.sub.209, and R.sub.210 include the same as
those of the alkyl group and the cycloalkyl group as R.sub.201,
R.sub.202, and R.sub.203 in the general formula (ZI'-2).
[0256] Examples of the alkylene group of A include an alkylene
group having 1 to 12 carbon atoms (for example, a methylene group,
an ethylene group, a propylene group, an isopropylene group, a
butylene group, an isobutylene group, and the like); examples of
the alkenylene group of A include an alkenylene group having 2 to
12 carbon atoms (for example, an ethenylene group, a propenylene
group, a butenylene group, and the like); and examples of the
arylene group of A include an arylene group having 6 to 10 carbon
atoms (for example, a phenylene group, a tolylene group, a
naphthylene group, and the like).
[0257] Particularly preferable examples of the acid generator to be
used in combination with the other components, which can be used in
combination with the compound (ZI'-3) of the present invention will
be shown below.
##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048##
##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053##
##STR00054##
[0258] The content of the acid generator which can be used in
combination of the compound (ZI-3) in the present invention in the
entire composition is preferably from 0.1 to 30% by mass, more
preferably from 0.5 to 25% by mass, and still more preferably 5 to
20% by mass, based on all the solids.
[0259] The amount of the acid generator when an acid generator to
be used in combination with the other components, besides the
compound (ZI-3) and the compound (ZI-3) is usually from 99/1 to
20/80, preferably 99/1 to 40/60, and still more preferably 99/1 to
50/50, in terms of a molar ratio (compound (ZI-3)/acid generator to
be used in combination with the other components).
[0260] [3] Hydrophobic Resin (C)
[0261] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention may include a hydrophobic
resin (C).
[0262] The resin (C) preferably contains at least any one of a
fluorine atom and a silicon atom. At least any one of such a
fluorine atom and a silicon atom in the resin (C) may be contained
in the main chain or the side chain of the resin.
[0263] In the case where the resin (C) contains a fluorine atom,
the fluorine atom-containing partial structure is preferably a
resin having a fluorine atom-containing alkyl group, a fluorine
atom-containing cycloalkyl group, or a fluorine atom-containing
aryl group.
[0264] The alkyl group containing a fluorine atom is a linear or
branched alkyl group in which at least one hydrogen atom is
substituted with a fluorine atom, preferably having 1 to 10 carbon
atoms, and more preferably 1 to 4 carbon atoms, and may have
another substituent.
[0265] The cycloalkyl group containing a fluorine atom is a
monocyclic or polycyclic cycloalkyl group in which at least one
hydrogen atom is substituted with a fluorine atom, and may have
another substituent.
[0266] Examples of the fluorine atom-containing aryl group include
an aryl group such as a phenyl, a naphthyl group, and the like, in
which at least one hydrogen atom is substituted with a fluorine
atom, and may have another substituent.
[0267] Preferable examples of the fluorine atom-containing alkyl
group, the fluorine atom-containing cycloalkyl group, and the
fluorine atom-containing aryl group include a group represented by
any one of the following general formulae (F2) to (F4), but the
present invention is not limited thereto.
##STR00055## [0268] In the general formulae (F2) to (F4), [0269]
each of R.sub.57 to R.sub.68 independently represents a hydrogen
atom, a fluorine atom, or an (linear or branched) alkyl group,
provided that at least one of R.sub.57 to R.sub.61, at least one of
R.sub.62 to R.sub.64, and at least one of R.sub.65 to R.sub.68
represents a fluorine atom, or an alkyl group (preferably having 1
to 4 carbon atoms) having at least one hydrogen atom thereof
substituted with a fluorine atom.
[0270] It is preferable that all of R.sub.57 to R.sub.61 and
R.sub.65 to R.sub.67 be fluorine atoms. R.sub.62, R.sub.63, and
R.sub.68 are preferably fluoroalkyl groups (preferably having 1 to
4 carbon atoms), and more preferably perfluoroalkyl groups having 1
to 4 carbon atoms. When R.sub.62 and R.sub.63 are perfluoroalkyl
groups, R.sub.64 is preferably a hydrogen atom. R.sub.62 and
R.sub.63 may be bonded to each other to form a ring.
[0271] Specific examples of the group represented by the general
formula (F2) include a p-fluorophenyl group, a pentafluorophenyl
group, a 3,5-di(trifluoromethyl)phenyl group and the like.
[0272] Specific examples of the group represented by the general
formula (F3) include a trifluoromethyl group, a pentafluoropropyl
group, a pentafluoroethyl group, a heptafluorobutyl group, a
hexafluoroisopropyl group, a heptafluoroisopropyl group, a
hexafluoro(2-methyl)isopropyl group, a nonafluorobutyl group, an
octafluoroisobutyl group, a nonafluorohexyl group, a
nonafluoro-t-butyl group, a perfluoroisopentyl group, a
perfluorooctyl group, a perfluoro(trimethyl)hexyl group, a
2,2,3,3-tetrafluorocyclobutyl group, a perfluorocyclohexyl group
and the like. A hexafluoroisopropyl group, a heptafluoroisopropyl
group, a hexafluoro(2-methyl)isopropyl group, an octafluoroisobutyl
group, a nonafluoro-t-butyl group, and a perfluoroisopentyl group
are preferred, and a hexafluoroisopropyl group and a
heptafluoroisopropyl group are more preferred.
[0273] Specific examples of the group represented by the general
formula (F4) include --C(CF.sub.3).sub.2OH,
--C(C.sub.2F.sub.5).sub.2OH, --C(CF.sub.3)(CF.sub.3)OH,
--CH(CF.sub.3)OH, and the like, and --C(CF.sub.3).sub.2OH is
preferred.
[0274] The fluorine atom-containing partial structure may be bonded
directly to the main chain or may be bonded to the main chain
through a group selected from the group consisting of an alkylene
group, a phenylene group, an ether bond, a thioether bond, a
carbonyl group, an ester bond, an amide bond, a urethane bond, and
a ureylene bond, or a group formed by combination of two or more of
these groups and bonds.
[0275] Examples of the preferable fluorine atom-containing
repeating unit will be shown below.
##STR00056##
[0276] In the formulae, each of R.sub.10 and R.sub.11 independently
represents a hydrogen atom, a fluorine atom, or an alkyl group. The
alkyl group is preferably a linear or branched alkyl group having 1
to 4 carbon atoms, and may have a substituent, and examples of the
alkyl group having a substituent includes, in particular, a
fluorinated alkyl group.
[0277] Each of W.sub.3 to W.sub.6 independently represents an
organic group having at least one or more fluorine atoms. Specific
examples thereof include the atomic groups of (F2) to (F4)
above.
[0278] Furthermore, the resin (C) may further contain, in addition
to these, the units as shown below, as a fluorine atom-containing
repeating unit.
##STR00057##
[0279] In the formulae, each of R.sub.4 to R.sub.7 independently
represents a hydrogen atom, a fluorine atom, or an alkyl group. The
alkyl group is preferably a linear or branched alkyl group having 1
to 4 carbon atoms and may have a substituent, and examples of the
alkyl group having a substituent includes, in particular, a
fluorinated alkyl group.
[0280] However, at least one of R.sub.4 to R.sub.7 represents a
fluorine atom. R.sub.4 and R.sub.5 or R.sub.6 and R.sub.7 may form
a ring.
[0281] W.sub.2 represents an organic group containing at least one
fluorine atom. Specific examples thereof include the atomic groups
of (F2) to (F4) above.
[0282] L.sub.2 represents a single bond or a divalent linking
group. The divalent linking group is a substituted or unsubstituted
arylene group, a substituted or unsubstituted alkylene group, a
substituted or unsubstituted cycloalkylene group, --O--,
--SO.sub.2--, --CO--, --N(R)-- (wherein R represents a hydrogen
atom or an alkyl group), --NHSO.sub.2--, or a divalent linking
group formed by combination of a plurality of these groups.
[0283] Q represents an alicyclic structure. The alicyclic structure
may have a substituent and may be monocyclic or polycyclic, and in
the case of a polycyclic structure, the structure may be a
crosslinked structure. The monocyclic structure is preferably a
cycloalkyl group having 3 to 8 carbon atoms, and examples thereof
include a cyclopentyl group, a cyclohexyl group, a cyclobutyl
group, a cyclooctyl group, and the like. Examples of the polycyclic
structure include a group containing a bicyclo structure, a
tricyclo structure, a tetracyclo structure, and the like, having 5
or more carbon atoms. A cycloalkyl group having 6 to 20 carbon
atoms is preferred, and examples thereof include an adamantyl
group, a norbornyl group, a dicyclopentyl group, a tricyclodecanyl
group, a tetracyclododecyl group, and the like. A part of carbon
atoms in the cycloalkyl group may be substituted with a heteroatom
such as an oxygen atom and the like. Particularly preferable
examples of Q include a norbornyl group, a tricyclodecanyl group, a
tetracyclododecyl group, and the like.
[0284] The resin (C) may contain a silicon atom.
[0285] The resin preferably has an alkylsilyl structure (preferably
a trialkylsilyl group) or a cyclic siloxane structure as the
silicon atom-containing partial structure.
[0286] Specific examples of the alkylsilyl structure and the cyclic
siloxane structure include the groups represented by the following
general formulae (CS-1) to (CS-3), and the like.
##STR00058## [0287] In the general formulae (CS-1) to (CS-3),
[0288] each of R.sub.12 to R.sub.26 independently represents a
linear or branched alkyl group (preferably having 1 to 20 carbon
atoms) or a cycloalkyl group (preferably having 3 to 20 carbon
atoms), [0289] each of L.sub.3 to L.sub.5 represents a single bond
or a divalent linking group, and examples of the divalent linking
group include a sole group or a combination of two or more groups
selected from the group consisting of an alkylene group, a
phenylene group, an ether bond, a thioether bond, a carbonyl group,
an ester bond, an amide bond, a urethane bond, and a ureylene bond,
and [0290] n represents an integer of 1 to 5, and n is preferably
an integer of 2 to 4.
[0291] The repeating unit having at least either a fluorine atom or
a silicon atom is preferably a (meth)acrylate-based repeating
unit.
[0292] Specific examples of the repeating unit having at least
either a fluorine atom or a silicon atom will be shown below, but
the present invention is not limited thereto. Further, in the
specific examples, X.sub.1 represents a hydrogen atom, --CH.sub.3,
--F, or --CF.sub.3, and X.sub.2 represents --F or --CF.sub.3.
##STR00059## ##STR00060## ##STR00061## ##STR00062##
##STR00063##
[0293] The resin (C) preferably contains (b) a repeating unit
having at least one group selected from the group consisting of
following (x) to (z): [0294] (x) an alkali-soluble group, [0295]
(y) a group which decomposes by the action of an alkaline developer
to increase the solubility in an alkaline developer (hereinafter
also referred to as "polarity converting group"), and [0296] (z) a
group which decomposes by the action of an acid to increase the
solubility in an alkaline developer.
[0297] The repeating unit (b) includes the following types. [0298]
(b') a repeating unit having at least either a fluorine atom or a
silicon atom and at least one group selected from the group
consisting of (x) to (z) above, on one side chain, [0299] (b*) a
repeating unit having at least one group selected from the group
consisting of (x) to (z) above and having neither a fluorine atom
nor a silicon atom, and [0300] (b'') a repeating unit having at
least one group selected from the group consisting of (x) to (z)
above on one side chain and at the same time, having at least
either a fluorine atom or a silicon atom on a side chain different
from the side chain above in the same repeating unit.
[0301] The resin (C) more preferably contains a repeating unit (b')
as the repeating unit (b). That is, it the repeating unit (b)
having at least one group selected from the group consisting of (x)
to (z) above still more preferably has at least either a fluorine
atom or a silicon atom.
[0302] In the case where the resin (C) contains the repeating unit
(b*), the resin is preferably a copolymer with a repeating unit
having at least either a fluorine atom or a silicon atom (a
repeating unit different from the repeating units (b') and (b'')
above). Further, in the repeating unit (b''), the side chain having
at least one group selected from the group consisting of (x) to (z)
and the side chain having at least either a fluorine atom or a
silicon atom are preferably bonded to the same carbon atom in the
main chain, that is, have a positional relationship like the
following formula (K1).
[0303] In the formula, B1 represents a partial structure having at
least one group selected from the group consisting of (x) to (z),
and B2 represents a partial structure having at least either a
fluorine atom or a silicon atom.
##STR00064##
[0304] The group selected from the group consisting of (x) to (z)
is preferably (x) an alkali-soluble group or a polarity converting
group (y), and more preferably a polarity converting group (y).
[0305] Examples of the alkali-soluble group (x) include a phenolic
hydroxyl group, a carboxylic acid group, a fluorinated alcohol
group, a sulfonic acid group, a sulfonamido group, a sulfonylimido
group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an
(alkylsulfonyl)(alkylcarbonyl)imido group, a
bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imido group,
a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imido
group, a tris(alkylcarbonyl)methylene group, a
tris(alkylsulfonyl)methylene group, and the like.
[0306] Preferred alkali-soluble groups include a fluorinated
alcohol group (preferably hexafluoroisopropanol), a sulfonimido
group and a bis(carbonyl)methylene group.
[0307] The repeating unit (bx) having (x) an alkali-soluble group
contains a repeating unit where an alkali-soluble group is directly
bonded to the main chain of the resin, such as a repeating unit of
an acrylic acid or a methacrylic acid; a repeating unit where an
alkali-soluble group is bonded to the main chain of the resin
through a linking group; and the like. Further, an alkali-soluble
group may be introduced into the polymer chain terminal by using an
alkali-soluble group-containing polymerization initiator or chain
transfer agent at the polymerization. All of these cases are
preferable.
[0308] In the case where the repeating unit (bx) is a repeating
unit having at least either a fluorine atom or a silicon atom (that
is, a repeating unit corresponding to the repeating unit (b') or
(b'')), examples of the fluorine atom-containing partial structure
in the repeating unit (bx) are the same as those in the
above-described repeating unit having at least either a fluorine
atom or a silicon atom, and the groups represented by the general
formulae (F2) to (F4) are preferred. Further, examples of the
silicon atom-containing partial structure in the repeating unit
(bx) include the same as those in the above-described repeating
unit having at least either a fluorine atom or a silicon atom, and
the groups represented by the general formulae (CS-1) to (CS-3) are
preferred.
[0309] The content of the repeating unit (bx) having an
alkali-soluble group (x) is preferably from 1 to 50 mol %, more
preferably from 3 to 35 mol %, and still more preferably from 5 to
20 mol %, based on all the repeating units in the resin (C).
[0310] Specific examples of the repeating unit (bx) having (x) an
alkali-soluble group are illustrated below, but the present
invention is not limited thereto [0311] In the formulae, Rx
represents H, CH.sub.3, CF.sub.3, or CH.sub.2OH
##STR00065## ##STR00066## ##STR00067##
[0312] In the following formulae, X.sub.1 represents H, CH.sub.3,
CF.sub.3, or CH.sub.2OH.
##STR00068##
[0313] Examples of the polarity converting group (y) include a
lactone group, a carboxylic ester group (--COO--), an acid
anhydride group (--C(O)OC(O)--), an acid imido group (--NHCONH--),
a carboxylic acid thioester group (--COS--), a carbonic ester group
(--OC(O)O--), a sulfuric ester group (--OSO.sub.2O--), a sulfonic
ester group (--SO.sub.2O), and the like, with a lactone group being
preferred.
[0314] As for the polarity converting group (y), both of an
embodiment where the group is contained, for example, in a
repeating unit of an acrylic ester or a methacrylic ester and
thereby is introduced into the side chain of the resin, and an
embodiment where the group is introduced into the terminal of the
polymer chain by using a polymerization initiator or chain transfer
agent having a polarity converting group (y), are preferable.
[0315] Specific examples of the repeating unit (by) having a
polarity converting group (y) include repeating units having a
lactone structure represented by formulae (KA-1-1) to (KA-1-17)
described later.
[0316] The repeating unit (by) having a polarity converting group
(y) is preferably a repeating unit having at least either a
fluorine atom or a silicon atom (that is, a repeating unit
corresponding to the repeating unit (b') or (b'')). The resin
containing the repeating unit (by) has hydrophobicity, and this is
preferable, particularly in view of reduction of development
defect.
[0317] Examples of the repeating unit (by) include a repeating unit
represented by the general formula (K0).
##STR00069## [0318] In the formula, R.sub.k1 represents a hydrogen
atom, a halogen atom, a hydroxyl group, an alkyl group, a
cycloalkyl group, an aryl group, or a polarity converting
group-containing group, and [0319] R.sub.k2 represents an alkyl
group, a cycloalkyl group, an aryl group, or a polarity converting
group-containing group.
[0320] However, at least either one of R.sub.k1 and R.sub.k2
represents a polarity converting group-containing group.
[0321] The polarity converting group indicates a group which
decomposes by the action of an alkaline developer to increase the
solubility in an alkaline developer, as described above. The
polarity converting group is preferably a group X in a partial
structure represented by the general formula (KA-1) or (KB-1)
##STR00070## [0322] In general formulae (KA-1) and (KB-1), [0323] X
represents a carboxylic ester group: --COO--, an acid anhydride
group: --C(O)OC(O)--, an acid imido group: --NHCONH--, a carboxylic
acid thioester group: --COS--, a carbonic ester group: --OC(O)O--,
a sulfuric ester group: --OSO.sub.2O--, or a sulfonic ester group:
--SO.sub.2O--, and [0324] each of Y.sup.1 and Y.sup.2 which may be
the same as or different from each other, represents an
electron-withdrawing group.
[0325] Moreover, the repeating unit (by) contains a group having a
partial structure represented by the general formula (KA-1) or
(KB-1) and thereby has a preferable group capable of increasing the
solubility in an alkaline developer, and as in the case of the
partial structure represented by the general formula (KA-1) or the
partial structure represented by (KB-1) where Y.sup.1 and Y.sup.2
are monovalent, when the partial structure does not have a bond,
the group having the partial structure is a group having a
monovalent or higher valent group formed by removing at least one
arbitrary hydrogen atom in the partial structure.
[0326] The partial structure represented by the general formula
(KA-1) or (KB-1) is connected to the main chain of the resin (C) at
an arbitrary position through a substituent.
[0327] The partial structure represented by the general formula
(KA-1) is a structure forming a ring structure together with the
group as X.
[0328] In the formula (KA-1), X is preferably a carboxylic ester
group (that is, a case of forming a lactone ring structure as
KA-1), an acid anhydride group or a carbonic ester group, and more
preferably a carboxylic ester group.
[0329] The ring structure represented by the general formula (KA-1)
may have a substituent and, for example, may have nka substituents
Z.sub.ka1.
[0330] When a plurality of Z.sub.ka1's are present, each of them
independently represents a halogen atom, an alkyl group, a
cycloalkyl group, an ether group, a hydroxyl group, an amido group,
an aryl group, a lactone ring group or an electron-withdrawing
group.
[0331] Z.sub.ka1's may be combined with each other to form a ring.
Examples of the ring formed by mutual linking of Z.sub.ka1's
include a cycloalkyl ring and a heterocyclic ring (for example, a
cyclic ether ring, a lactone ring, and the like).
[0332] nka represents an integer of 0 to 10, preferably an integer
of 0 to 8, more preferably an integer of 0 to 5, still more
preferably an integer of 1 to 4, and most preferably an integer of
1 to 3.
[0333] The electron-withdrawing group as Z.sub.ka1 has the same
meaning as the electron-withdrawing group of Y.sup.1 and Y.sup.2 as
described later. The electron-withdrawing group above may be
substituted with another electron-withdrawing group.
[0334] Z.sub.ka1 is preferably an alkyl group, a cycloalkyl group,
an ether group, a hydroxyl group or an electron-withdrawing group,
more preferably an alkyl group, a cycloalkyl group or an
electron-withdrawing group. The ether group is preferably an ether
group substituted, for example, with an alkyl group or a cycloalkyl
group, that is, an alkyl ether group, or the like. The
electron-withdrawing group has the same meaning as above.
[0335] Examples of the halogen atom as Z.sub.ka1 include a fluorine
atom, a chlorine atom, a bromine atom, an iodine atom, and the like
with a fluorine atom being preferred.
[0336] The alkyl group as Z.sub.ka1 may have a substituent and may
be either linear or branched. The linear alkyl group is preferably
an alkyl group having 1 to 30 carbon atoms, and more preferably 1
to 20 carbon atoms, and examples thereof include a methyl group, an
ethyl group, an n-propyl group, an n-butyl group, a sec-butyl
group, a t-butyl group, an n-pentyl group, an n-hexyl group, an
n-heptyl group, an n-octyl group, an n-nonyl group, an n-decanyl
group, and the like. The branched alkyl group is preferably an
alkyl group having 3 to 30 carbon atoms, and more preferably 3 to
20 carbon atoms, and examples thereof include an i-propyl group, an
i-butyl group, a t-butyl group, an i-pentyl group, a t-pentyl
group, an i-hexyl group, a t-hexyl group, an i-heptyl group, a
t-heptyl group, an i-octyl group, a t-octyl group, an i-nonyl
group, a t-decanoyl group, and the like. An alkyl group having 1 to
4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl
group, an i-propyl group, an n-butyl group, an i-butyl group, a
t-butyl group, and the like, is preferable.
[0337] The cycloalkyl group as Z.sub.ka1 may have a substituent and
may be monocyclic or polycyclic, and in the case of polycyclic, the
cycloalkyl group may be a crosslinked cycloalkyl group. That is, in
this case, the cycloalkyl group may have a bridged structure. The
monocyclic cycloalkyl group is preferably a cycloalkyl group having
3 to 8 carbon atoms, and examples thereof include a cyclopropyl
group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group,
a cyclooctyl group, and the like. The polycyclic cycloalkyl group
includes a group having a bicyclo structure, a tricyclo structure,
a tetracyclo structure, and the like and having 5 or more carbon
atoms, and a cycloalkyl group having 6 to 20 carbon atoms is
preferable. Examples thereof include an adamantyl group, a
norbornyl group, an isobornyl group, a camphanyl group, a
dicyclopentyl group, an .alpha.-pinel group, a tricyclodecanyl
group, a tetracyclododecyl group, and an androstanyl group. As the
cycloalkyl group, structures shown below are also preferable.
Incidentally, a part of carbon atoms in the cycloalkyl group may be
substituted for by a heteroatom such as an oxygen atom and the
like.
##STR00071## ##STR00072## ##STR00073## ##STR00074##
[0338] Preferable examples of the alicyclic moiety include an
adamantyl group, a noradamantyl group, a decalin group, a
tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl
group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a
cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.
An adamantyl group, a decalin group, a norbornyl group, a cedrol
group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group,
a cyclodecanyl group, a cyclododecanyl group and a tricyclodecanyl
group are more preferred.
[0339] The substituent of the alicyclic structure includes an alkyl
group, a halogen atom, a hydroxyl group, an alkoxy group, a
carboxyl group and an alkoxycarbonyl group. The alkyl group is
preferably a lower alkyl group such as a methyl group, an ethyl
group, a propyl group, an isopropyl group, a butyl group, and the
like, and more preferably a methyl group, an ethyl group, a propyl
group or an isopropyl group. The alkoxy group is preferably an
alkoxy group having 1 to 4 carbon atoms, such as a methoxy group,
an ethoxy group, a propoxy group, a butoxy group, and the like.
Examples of the substituent which the alkyl group and alkoxy group
may have include a hydroxyl group, a halogen atom, an alkoxy group
(preferably having 1 to 4 carbon atoms), and the like.
[0340] Furthermore, the groups above may further have a
substituent, and examples of the further substituent include a
hydroxyl group, a halogen atom (for example, fluorine, chlorine,
bromine, and iodine), a nitro group, a cyano group, the
above-described alkyl group, an alkoxy group such as a methoxy
group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a
hydroxypropoxy group, an n-butoxy group, an isobutoxy group, a
sec-butoxy group, a t-butoxy group, and the like, an alkoxycarbonyl
group such as a methoxycarbonyl group, an ethoxycarbonyl group, and
the like, an aralkyl group such as a benzyl group, a phenethyl
group, a cumyl group, and the like, an acyl group such as an
aralkyloxy group, a formyl group, an acetyl group, a butyryl group,
a benzoyl group, a cinnamyl group, a valeryl group, and the like,
an acyloxy group such as a butyryloxy group and the like, the
above-described alkenyl group, an alkenyloxy group such as a
vinyloxy group, a propenyloxy group, an allyloxy group, a
butenyloxy group, and the like, the above-described aryl group, an
aryloxy group such as a phenoxy group and the like, and an
aryloxycarbonyl group such as a benzoyloxy group and the like.
[0341] It is preferable that X in the general formula (KA-1) be a
carboxylic ester group and the partial structure represented by the
general formula (KA-1) be a lactone ring, and preferably a 5- to
7-membered lactone ring.
[0342] Incidentally, it is preferable that as in (KA-1-1) to
(KA-1-17) shown below, another ring structure is condensed to a 5-
to 7-membered lactone ring as the partial structure represented by
the general formula (KA-1) in the form of forming a bicyclo or
spiro structure.
[0343] Examples of the peripheral ring structure with which the
ring structure represented by the general formula (KA-1) may be
combined include those in (KA-1-1) to (KA-1-17) shown below and
structures based on these structures.
[0344] The structure containing a lactone ring structure
represented by the general formula (KA-1) is more preferably a
structure represented by any one of the following (KA-1-1) to
(KA-1-17). Further, the lactone structure may be bonded directly to
the main chain. Preferred structures are (KA-1-1), (KA-1-4),
(KA-1-5), (KA-1-6), (KA-1-13), (KA-1-14), and (KA-1-17).
##STR00075## ##STR00076##
[0345] The structure containing the above-described lactone ring
structure may or may not have a substituent. Preferable examples of
the substituent are the same as those of the substituent Z.sub.ka1
which may be contained in the ring structure represented by the
general formula (KA-1)
[0346] In the general formula (KB-1), X preferably includes a
carboxylic ester group (--COO--).
[0347] In the general formula (KB-1), each of Y.sup.1 and Y.sup.2
independently represents an electron-withdrawing group.
[0348] The electron-withdrawing group is a partial structure
represented by the following formula (EW). In the formula (EW), *
represents a bond directly bonded to (KA-1) or a bond directly
bonded to X in (KB-1).
##STR00077## [0349] In the formula (EW), [0350] n.sub.ew is a
repetition number of the linking group represented by
--C(R.sub.ew1)(R.sub.ew2)--, and represents an integer of 0 or 1.
In the case where n.sub.ew is 0, this indicates bonding by a single
bond and direct bonding of Y.sub.ew1.
[0351] Y.sub.ew1 is a halogen atom, a cyano group, a nitrile group,
a nitro group, a halo(cyclo)alkyl, a haloaryl group represented by
--C(R.sub.f1)(R.sub.f2)--R.sub.f3, an oxy group, a carbonyl group,
a sulfonyl group, a sulfinyl group, or a combination thereof.
Further, the electron-withdrawing group may be, for example, a
structure shown below. The "halo(cyclo)alkyl group" indicates an
alkyl or cycloalkyl group that is at least partially halogenated.
The term "haloaryl group" indicates an aryl group that is at least
partially halogenated. In the structural formulae below, each of
R.sub.ew3 and R.sub.ew4 independently represents an arbitrary
structure. The partial structure represented by the general formula
(EW) has an electron-withdrawing property irrespective of
structures of R.sub.ew3 and R.sub.ew4 and may be combined with, for
example, the main chain of the resin, but is preferably an alkyl
group, a cycloalkyl group, or an alkyl fluoride group.
##STR00078##
[0352] In the case where Y.sub.ew1 is a divalent or higher-valent
group, the remaining bond forms bonding to an arbitrary atom or
substituent. At least any one group of Y.sub.ew1, R.sub.ew1, and
R.sub.ew2 may be combined with the main chain of a resin (C)
through a further substituent.
[0353] Y.sub.ew1 is preferably a halogen atom, or a
halo(cyclo)alkyl or haloaryl group represented by
--C(R.sub.f1)(R.sub.f2)--R.sub.f3.
[0354] Each of R.sub.ew1 and R.sub.ew2 independently represents an
arbitrary substituent, and represents, for example, a hydrogen
atom, an alkyl group, a cycloalkyl group, or an aryl group.
[0355] At least two of R.sub.ew1, R.sub.ew2, and Y.sub.ew1 may be
combined with each other to form a ring.
[0356] Here, R.sub.f1 represents a halogen atom, a perhaloalkyl
group, a perhalocycloalkyl group or a perhaloaryl group and is
preferably a fluorine atom, a perfluoroalkyl group, or a
perfluorocycloalkyl group, and more preferably a fluorine atom or a
trifluoromethyl group.
[0357] Each of R.sub.f2 and R.sub.f3 independently represents a
hydrogen atom, a halogen atom or an organic group, and R.sub.f2 and
R.sub.f3 may be combined with each other to form a ring. Examples
of the organic group include an alkyl group, a cycloalkyl group, an
alkoxy group, and the like. R.sub.f2 preferably represents the same
group as R.sub.f1 or is combined with R.sub.f3 to form a ring.
[0358] R.sub.f1 to R.sub.f3 may be combined with each other to form
a ring, and examples of the ring formed include a (halo)cycloalkyl
ring, a (halo)aryl ring, and the like.
[0359] Examples of the (halo)alkyl group in R.sub.f1 to R.sub.f3
include the alkyl groups in Z.sub.ka1 and halogenated structures
thereof.
[0360] Examples of the (per)halocycloalkyl group and the
(per)haloaryl group in the ring formed by combination of R.sub.f2
and R.sub.f3 in R.sub.f1 to R.sub.f3 include structures resulting
from halogenation of cycloalkyl groups in Z.sub.ka1, and a
fluoroalkyl group represented by --C.sub.(n)F.sub.(2n-2)H and a
perfluoroaryl group represented by --C.sub.(n)F.sub.(n-1) are
preferable, where the carbon number n is not particularly limited
but is preferably from 5 to 13, and more preferably 6.
[0361] The ring which may be formed by combination of at least two
of R.sub.ew1, R.sub.ew2, and Y.sub.ew1 with each other is
preferably a cycloalkyl group or a heterocyclic group, and the
heterocyclic group is preferably a lactone ring group. Examples of
the lactone ring include structures represented by the formulae
(KA-1-1) to (KA-1-17).
[0362] Incidentally, the repeating unit (by) may have a plurality
of partial structures represented by the general formula (KA-1), a
plurality of partial structures represented by the general formula
(KB-1), or both a partial structure represented by the general
formula (KA-1) and a partial structure represented by the general
formula (KB-1).
[0363] Further, the partial structure of the general formula (KA-1)
may partially or entirely serve also as the electron-withdrawing
group of Y.sup.1 or Y.sup.2 in the general formula (KB-1). For
example, in the case where X in the general formula (KA-1) is a
carboxylic ester group, the carboxylic ester group may function as
the electron-withdrawing group of Y.sup.1 or Y.sup.2 in the general
formula (KB-1).
[0364] Moreover, in the case where the repeating unit (by) comes
under the repeating unit (b*) or the repeating unit (b'') and has a
partial structure represented by the general formula (KA-1), the
partial structure represented by the general formula (KA-1) is more
preferably a partial structure where the polarity converting group
is --COO-- in the structure represented by the general formula
(KA-1). The repeating unit (by) is more preferably a repeating unit
having a partial structure shown below.
[0365] The repeating unit (by) may be a repeating unit having a
partial structure represented by the general formula (KY-0)
##STR00079## [0366] In the general formula (KY-0), [0367] R.sub.2
represents a chained or cyclic alkylene group and when a plurality
of R.sub.2's are present, they may be the same as or different from
each other, [0368] R.sub.3 represents a linear, branched, or cyclic
hydrocarbon group where a part or all of hydrogen atoms on the
constituent carbons are substituted with a fluorine atom, [0369]
R.sub.4 represents a halogen atom, a cyano group, a hydroxyl group,
an amido group, an alkyl group, a cycloalkyl group, an alkoxy
group, a phenyl group, an acyl group, an alkoxycarbonyl group, or a
group represented by R--C(.dbd.O)-- or R--C(.dbd.O)O-- (wherein R
represents an alkyl group or a cycloalkyl group), and when a
plurality of R.sub.4's are present, they may be the same as or
different from each other, and two or more R.sub.4's may be bonded
to each other to form a ring, [0370] X represents an alkylene
group, an oxygen atom, or a sulfur atom, [0371] each of Z and Za
represents a single bond, an ether bond, an ester bond, an amide
bond, a urethane bond, or a urea bond, and when a plurality of Z's
or Za's are present, they may be the same as or different from each
other, [0372] * represents a bond to the main chain or side chain
of the resin.
[0373] o is the number of substituents and represents an integer of
1 to 7, [0374] m is the number of substituents and represents an
integer of 0 to 7, and [0375] n is a repetition number and
represents an integer of 0 to 5.
[0376] The structure of --R.sub.2--Z-- is preferably a structure
represented by --(CH.sub.2).sub.1--COO-- (wherein 1 represents an
integer of 1 to 5).
[0377] The preferable range of carbon number and specific examples
of the chained or cyclic alkylene group as R.sub.2 are the same as
those described for the chained alkylene group and cyclic alkylene
group in Z.sub.2 of the general formula (bb).
[0378] The carbon number of the linear, branched, or cyclic
hydrocarbon group as R.sub.3 is, in the case of a linear
hydrocarbon group, preferably from 1 to 30, and more preferably
from 1 to 20, in the case of a branched hydrocarbon group,
preferably from 3 to 30, and more preferably from 3 to 20, and in
the case of a cyclic hydrocarbon group, from 6 to 20. Specific
examples of R.sub.3 include specific examples of the alkyl group
and a cycloalkyl group as Z.sub.ka1.
[0379] The preferable carbon numbers and specific examples of the
alkyl group and a cycloalkyl group as R.sub.4 and R are the same as
those described with respect to the alkyl group and the cycloalkyl
group as Z.sub.ka1.
[0380] The acyl group as R.sub.4 is preferably an acyl group having
1 to 6 carbon atoms, and examples thereof include a formyl group,
an acetyl group, a propionyl group, a butyryl group, an isobutyryl
group, a valeryl group, a pivaloyl group, and the like.
[0381] The alkyl moiety in the alkoxy group and the alkoxycarbonyl
group as R.sub.4 include a linear, branched, or cyclic alkyl
moiety, and the preferable carbon number and specific examples of
the alkyl moiety are the same as those described for the alkyl
group and the cycloalkyl group of Z.sub.ka1.
[0382] The alkylene group as X includes a chained or cyclic
alkylene group, and the preferable carbon number and specific
examples thereof are the same as those described for the chained
alkylene group and the cyclic alkylene group as R.sub.2.
[0383] Further, the specific structure of the repeating unit (by)
also contains a repeating unit having a partial structure shown
below.
##STR00080## [0384] In the general formula (rf-1) and (rf-2),
[0385] X' represents an electron-withdrawing substituent and is
preferably a carbonyloxy group, an oxycarbonyl group, a fluorine
atom-substituted alkylene group, or a fluorine atom-substituted
cycloalkylene group, [0386] A represents a single bond, a divalent
linking group represented by --C(Rx)(Ry)-, wherein each of Rx and
Ry independently represents a hydrogen atom, a fluorine atom, an
alkyl group (preferably having 1 to 6 carbon atoms, which may be
substituted with a fluorine atom or the like), or a cycloalkyl
group (preferably having 5 to 12 carbon atoms, which may be
substituted with a fluorine atom or the like), and each of Rx and
Ry is preferably a hydrogen atom, an alkyl group, or a fluorine
atom-substituted alkyl group, [0387] X represents an
electron-withdrawing group and specific examples thereof include
the electron-withdrawing groups as Y.sup.1 and Y.sup.2, and X is
preferably an alkyl fluoride group, a cycloalkyl fluoride group, an
aryl group substituted with fluorine or an alkyl fluoride group, an
aralkyl group substituted with fluorine or an alkyl fluoride group,
a cyano group, or a nitro group, and [0388] * represents a bond to
the main chain or side chain of the resin, that is, a bond which is
bonded to the main chain of the resin through a single bond or a
linking group.
[0389] Incidentally, when X' is a carbonyloxy group or an
oxycarbonyl group, A is not a single bond.
[0390] The polarity converting group decomposes by the action of an
alkaline developer to effect polarity conversion, whereby the
receding contact angle with water of the resist film after alkali
development can be decreased. Decrease in the receding contact
angle with water of the film after alkali development is preferable
from the viewpoint of suppressing the development defect.
[0391] The receding contact angle with water of the resist film
after alkali development is preferably 50.degree. or less, more
preferably 40.degree. or less, still more preferably 35.degree. or
less, and most preferably 30.degree. or less, at a temperature of
23.+-.3.degree. C. and a humidity of 45.+-.5%.
[0392] The receding contact angle is a contact angle measured when
a contact line recedes on the liquid droplet-substrate interface,
and this is generally known to be useful in simulating the mobility
of a liquid droplet in the dynamic state. In a simple manner, the
receding contact angle can be defined as a contact angle at the
time of the liquid droplet interface receding when a liquid droplet
ejected from a needle tip is landed on a substrate and then the
liquid droplet is again suctioned into the needle. In general, the
receding contact angle can be measured by a contact angle measuring
method called an expansion/contraction method.
[0393] The receding contact angle of the film after alkali
development is a contact angle measured when a film shown below is
measured by the expansion/contraction method described in Examples
as described later. That is, it is a contact angle of a film
obtained as follows by measurement by an expansion/contraction
method: ARC29SR (available from Nissan Chemical Industries, Ltd.)
for forming an organic antireflection film was applied onto a
silicon wafer (8-inch opening) and baked at 205.degree. C. for 60
seconds, thereby forming an antireflection film having a film
thickness of 98 nm. The actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention was
applied thereonto and baked at 120.degree. C. for 60 seconds,
thereby forming a film having a film thickness of 120 nm. This film
was developed in an aqueous tetramethylammonium hydroxide solution
(2.38% by mass) for 30 seconds, rinsed with pure water, and then
spin-dried, thereby obtaining a film.
[0394] The hydrolysis rate of the resin (C) for an alkaline
developer is preferably 0.001 nm/sec or more, more preferably 0.01
nm/sec or more, still more preferably 0.1 nm/sec or more, and most
preferably 1 nm/sec or more.
[0395] The hydrolysis rate of the resin (C) for an alkaline
developer as used herein is the rate at which the thickness of a
resin film formed only of the resin (C) decreases when treated with
TMAH (an aqueous tetramethylammonium hydroxide solution) (2.38% by
mass) at 23.degree. C.
[0396] The repeating unit (by) is more preferably a repeating
having at least two or more polarity converting groups.
[0397] In the case where the repeating unit (by) has at least two
polarity converting groups, the repeating unit preferably has a
group containing a partial structure having two polarity converting
groups represented by the following general formula (KY-1).
Incidentally, when the structure represented by the general formula
(KY-1) does not have a bond, this is a group containing a
monovalent or higher valent group formed by removing at least one
arbitrary hydrogen atom in the structure.
##STR00081## [0398] In the general formula (KY-1), [0399] each of
R.sub.ky1 and R.sub.ky4 independently represents a hydrogen atom, a
halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group,
a carbonyloxy group, an oxycarbonyl group, an ether group, a
hydroxyl group, a cyano group, an amido group, or an aryl group.
Alternatively, R.sub.ky1 and R.sub.ky4 may be bonded to the same
atom to form a double bond. For example, R.sub.ky1 and R.sub.ky4
may be bonded to the same oxygen atom to form a part (.dbd.O) of a
carbonyl group.
[0400] Each of R.sub.ky2 and R.sub.ky3 independently represents an
electron-withdrawing group, or while R.sub.ky1 and R.sub.ky2 are
combined to form a lactone ring, R.sub.ky3 is an
electron-withdrawing group. The lactone ring formed is preferably a
structure of (KA-1-1) to (KA-1-17). Examples of the
electron-withdrawing group are the same as those for Y.sub.1 and
Y.sub.2 in the general formula (KB-1), and a halogen atom and a
halo(cyclo)alkyl or haloaryl group represented by
--C(R.sub.f1)(R.sub.f2)--R.sub.f3 are preferable. Preferably,
R.sub.ky3 is a halogen atom or a halo(cyclo)alkyl or haloaryl group
represented by --C(R.sub.f1)(R.sub.f2)--R.sub.f3, and R.sub.ky2 is
combined with R.sub.ky1 to form a lactone ring or is an
electron-withdrawing group containing no halogen atom.
[0401] R.sub.ky1, R.sub.ky2, and R.sub.ky4 may be combined with
each other to form a monocyclic or polycyclic structure.
[0402] Specific examples of R.sub.ky1 and R.sub.ky4 include the
same as those for Z.sub.ka1 in the formula (KA-1).
[0403] The lactone ring formed by combination of R.sub.ky1 and
R.sub.ky2 is preferably a structure of (KA-1-1) to (KA-1-17).
Examples of the electron-withdrawing group are the same as those
for Y.sub.1 and Y.sub.2 in the general formula (KB-1).
[0404] The structure represented by the general formula (KY-1) is
preferably a structure represented by the following general formula
(KY-2). Here, the structure represented by the general formula
(KY-2) is a group having a monovalent or higher valent group formed
by removing at least one arbitrary hydrogen atom in the
structure.
##STR00082## [0405] In the formula (KY-2), [0406] each of R.sub.ky6
to R.sub.ky10 independently represents a hydrogen atom, a halogen
atom, an alkyl group, a cycloalkyl group, a carbonyl group, a
carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl
group, a cyano group, an amido group, or an aryl group.
[0407] two or more members of R.sub.ky6 to R.sub.ky10 may be
combined with each other to form a monocyclic or polycyclic
structure, and [0408] R.sub.ky5 represents an electron-withdrawing
group, and examples of the electron-withdrawing group are the same
as those for Y.sub.1 and Y.sub.2, with a halogen atom and a
halo(cyclo)alkyl or haloaryl group represented by
--C(R.sub.f1)(R.sub.f2)--R.sub.f3 being preferred.
[0409] Specific examples of R.sub.ky5 to R.sub.ky10 include the
same as those for Z.sub.ka1 in the formula (KA-1).
[0410] The structure represented by the formula (KY-2) is more
preferably a partial structure represented by the following general
formula (KY-3).
##STR00083##
[0411] In the formula (KY-3), Z.sub.ka1 and n.sub.ka have the same
meanings as in the general formula (KA-1). R.sub.ky5 has the same
meaning as in the formula (KY-2).
[0412] L.sub.ky represents an alkylene group, an oxygen atom, or a
sulfur atom. Examples of the alkylene group of L.sub.ky include a
methylene group, an ethylene group, and the like. L.sub.ky is
preferably an oxygen atom or a methylene group, and more preferably
a methylene group.
[0413] The repeating unit (b) is not limited as long as it is a
repeating unit obtained by polymerization such as addition
polymerization, condensation polymerization and addition
condensation, but a repeating unit obtained by addition
polymerization of a carbon-carbon double bond is preferable.
Examples thereof include an acrylate-based repeating unit
(including a system having a substituent at the .alpha.- or
.beta.-position), a styrene-based repeating unit (including a
system having a substituent at the .alpha.- or .beta.-position), a
vinyl ether-based repeating unit, a norbornene-based repeating
unit, a maleic acid derivative (such as maleic anhydride or a
derivative thereof, maleimide, and the like) repeating unit, and
the like. An acrylate-based repeating unit, a styrene-based
repeating unit, a vinyl ether-based repeating unit and a
norbornene-based repeating unit are preferable, an acrylate-based
repeating unit, a vinyl ether-based repeating unit and a
norbornene-based repeating unit are more preferable, and an
acrylate-based repeating unit is most preferable.
[0414] In the case where the repeating unit (by) is a repeating
unit having at least either a fluorine atom or a silicon atom (that
is, a repeating unit corresponding to the repeating unit (b') or
(b'')), examples of the fluorine atom-containing partial structure
in the repeating unit (by) are the same as those in the
above-described repeating unit having at least either a fluorine
atom or a silicon atom, and the groups represented by the general
formulae (F2) to (F4) are preferable. Further, examples of the
silicon atom-containing partial structure in the repeating unit
(by) are the same as those in the above-described repeating unit
having at least either a fluorine atom or a silicon atom, and the
groups represented by the general formulae (CS-1) to (CS-3) are
preferable.
[0415] The content of the repeating unit (by) in the resin (C) is
preferably from 10 to 100 mol %, more preferably from 20 to 99 mol
%, still more preferably from 30 to 97 mol %, and most preferably
from 40 to 95 mol %, based on all the repeating units in the resin
(C).
[0416] Specific examples of the repeating unit (by) having a group
capable of increasing the solubility in an alkaline developer are
illustrated below, but the present invention is not limited
thereto. Specific examples of the repeating unit (by) also include
those described as specific examples of the repeating unit (a3) of
the resin (A).
[0417] Ra represents a hydrogen atom, a fluorine atom, a methyl
group, or a trifluoromethyl group.
##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088##
##STR00089##
[0418] Examples of the repeating unit (bz) having (z) a group which
decomposes by the action of an acid in the resin (C) are the
repeating units having an acid-decomposable group.
[0419] The acid-decomposable group preferably has a structure in
which the alkali-soluble group is protected with a group which
decomposes and is cleaved by the action of an acid.
[0420] Examples of the alkali-soluble group include a phenolic
hydroxyl group, a carboxyl group, a fluorinated alcohol group, a
sulfonic acid group, a sulfonamido group, a sulfonylimido group, an
(alkylsulfonyl)(alkylcarbonyl)methylene group, an
(alkylsulfonyl)(alkylcarbonyl)imido group, a
bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imido group,
a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imido
group, a tris(alkylcarbonyl)methylene group, a
tris(alkylsulfonyl)methylene group, and the like.
[0421] Preferable examples of the alkali-soluble group include a
carboxyl group, a fluorinated alcohol group (preferably a
hexafluoroisopropanol group), and a sulfonic acid group.
[0422] The acid-decomposable group is preferably a group as
obtained by substituting the hydrogen atom of any of these
alkali-soluble groups with an acid-cleavable group.
[0423] Examples of the acid-cleavable group include
--C(R.sub.36)(R.sub.37)(R.sub.38),
--C(R.sub.36)(R.sub.37)(OR.sub.39),
--C(R.sub.01)(R.sub.02)(OR.sub.39), and the like.
[0424] In the formulae, each of R.sub.36 to R.sub.39 independently
represents an alkyl group, a cycloalkyl group, an aryl group, an
aralkyl group, or an alkenyl group. R.sub.36 and R.sub.37 may be
bonded to each other to form a ring.
[0425] Each of R.sub.01 to R.sub.02 independently represents a
hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group,
an aralkyl group, or an alkenyl group.
[0426] The acid-decomposable group is preferably a cumyl ester
group, an enol ester group, an acetal ester group, a tertiary alkyl
ester group, and the like, and more preferably a tertiary alkyl
ester group.
[0427] In the case where the repeating unit (bz) is a repeating
unit having at least either a fluorine atom or a silicon atom (that
is, a repeating unit corresponding to the repeating unit (b') or
(b'')), examples of the fluorine atom-containing partial structure
in the repeating unit (bz) are the same as those in the
above-described repeating unit having at least either a fluorine
atom or a silicon atom, and the groups represented by the general
formulae (F2) to (F4) are preferred. Further, examples of the
silicon atom-containing partial structure in the repeating unit
(bz) include the same as those in the above-described repeating
unit having at least either a fluorine atom or a silicon atom, and
the groups represented by the general formulae (CS-1) to (CS-3) are
preferred.
[0428] The content of the repeating unit (bz) having (z) an
alkali-soluble group in the resin (C) is preferably from 1 to 80
mol %, more preferably from 10 to 80 mol %, and still more
preferably from 20 to 60 mol %, based on all the repeating units in
the resin (C).
[0429] While the repeating unit (b) having at least one group
selected from the group consisting of (x) to (z) is described
above, the content of the repeating unit (b) in the resin (C) is
preferably from 1 to 98 mol %, more preferably from 3 to 98 mol %,
still more preferably from 5 to 97 mol %, and most preferably from
10 to 95 mol %, based on all the repeating units in the resin
(C).
[0430] The content of the repeating unit (b') is preferably from 1
to 100 mol %, more preferably from 3 to 99 mol %, still more
preferably from 5 to 97 mol %, and most preferably from 10 to 95
mol %, based on all the repeating units in the resin (C).
[0431] The content of the repeating unit (b*) is preferably from 1
to 90 mol %, more preferably from 3 to 80 mol %, still more
preferably from 5 to 70 mol %, and most preferably from 10 to 60
mol %, based on all the repeating units in the resin (C). The
content of the repeating unit having at least either a fluorine
atom or a silicon atom, which is used together with the repeating
unit (b*), is preferably from 10 to 99 mol %, more preferably from
20 to 97 mol %, still more preferably from 30 to 95 mol %, and most
preferably from 40 to 90 mol %, based on all the repeating units in
the resin (C).
[0432] The content of the repeating unit (b'') is preferably from 1
to 100 mol %, more preferably from 3 to 99 mol %, still more
preferably from 5 to 97 mol %, and most preferably from 10 to 95
mol %, based on all the repeating units in the resin (C).
[0433] The resin (C) may contain a repeating unit represented by
the following general formula (CIII).
##STR00090## [0434] In the general formula (CIII), [0435] R.sub.c31
represents a hydrogen atom, an alkyl group, an alkyl group which
may be substituted with fluorine, a cyano group, or a
--CH.sub.2--O--R.sub.ac2 group, wherein R.sub.ac2 represents a
hydrogen atom, an alkyl group, or an acyl group, and R.sub.c31 is
preferably a hydrogen atom, a methyl group, a hydroxymethyl group,
or a trifluoromethyl group, and particularly preferably a hydrogen
atom or a methyl group, [0436] R.sub.c32 represents a group having
an alkyl group, a cycloalkyl group, an alkenyl group, or a
cycloalkenyl group, and each of these groups may be substituted
with a fluorine atom- or silicon atom-containing group, or the
like, and [0437] L.sub.c3 represents a single bond or a divalent
linking group.
[0438] The alkyl group of R.sub.c32 in the general formula (CIII)
is preferably a linear or branched alkyl group having 3 to 20
carbon atoms.
[0439] The cycloalkyl group is preferably a cycloalkyl group having
3 to 20 carbon atoms.
[0440] The alkenyl group is preferably an alkenyl group having 3 to
20 carbon atoms.
[0441] The cycloalkenyl group is preferably a cycloalkenyl group
having 3 to 20 carbon atoms.
[0442] The aryl group is preferably a phenyl group or a naphthyl
group, having 6 to 20 carbon atoms, and the group may have a
substituent.
[0443] R.sub.c32 is preferably an unsubstituted alkyl group or a
fluorine atom-substituted alkyl group.
[0444] The divalent linking group of L.sub.c3 is preferably an
alkylene group (preferably having 1 to 5 carbon atoms), an oxy
group, a phenylene group, or an ester bond (a group represented by
--COO--).
[0445] The resin (C) preferably further contains a repeating unit
represented by the following general formula (BII-AB).
##STR00091## [0446] In the formula (BII-AB), [0447] each of
R.sub.c11' and R.sub.c12' independently represents a hydrogen atom,
a cyano group, a halogen atom, or an alkyl group, and [0448]
Z.sub.c' represents an atomic group for forming an alicyclic
structure containing two carbon atoms (C--C) to which Z.sub.c' is
bonded.
[0449] In the case where each group in the repeating units
represented by the general formulae (III) and (BII-AB) are
substituted with a fluorine atom- or silicon atom-containing group,
the repeating unit corresponds also to the above-described
repeating unit having at least either a fluorine atom or a silicon
atom.
[0450] Specific examples of the repeating units represented by the
general formulae (III) and (BII-AB) are shown below, but the
present invention is not limited thereto. In the formulae, Ra
represents H, CH.sub.3, CH.sub.2OH, CF.sub.3, or CN. Incidentally,
the repeating unit where Ra is CF.sub.3 corresponds also to the
above-described repeating unit having at least either a fluorine
atom or a silicon atom.
##STR00092## ##STR00093## ##STR00094##
[0451] In the resin (C), similarly to the resin (A), it is of
course preferable that the content of impurities such as a metal
and the like is small, but also, the content of residual monomers
or oligomer components is preferably from 0 to 10% by mass, more
preferably from 0 to 5% by mass, still more preferably from 0 to 1%
by mass. When these conditions are satisfied, a resist composition
free from extraneous substances in a liquid or change with aging of
sensitivity or the like can be obtained. Furthermore, in view of
resolution, resist profile, side wall of resist pattern, roughness,
and the like, the molecular weight distribution (Mw/Mn, also
referred to as "polydispersity") is preferably in the range of 1 to
3, more preferably 1 to 2, still more preferably 1 to 1.8, and most
preferably 1 to 1.5.
[0452] As for the resin (C), various commercially available
products may be used, or the resin may be synthesized by a
conventional method (for example, radical polymerization). Examples
of the general synthesis method include a batch polymerization
method of dissolving monomer species and an initiator in a solvent
and heating the solution, thereby effecting the polymerization, and
a dropping polymerization method of adding dropwise a solution
containing monomer species and an initiator to a heated solvent
over 1 to 10 hours, and the like. A dropping polymerization method
is preferred.
[0453] The reaction solvent, the polymerization initiator, the
reaction conditions (for example, a temperature, a concentration,
and the like), and the purification method after reaction are the
same as those described for the resin (A).
[0454] Specific examples of the resin (C) will be shown below.
Further, the molar ratio of repeating units (corresponding to
repeating units starting from the left), the weight average
molecular weight, and the polydispersity of each resin are shown in
the Table below.
TABLE-US-00001 TABLE 1 Compositional ratio Polymer (mol %) Mw Mw/Mn
B-1 50/50 6000 1.5 B-2 30/70 6500 1.4 B-3 45/55 8000 1.4 B-4 100
15000 1.7 B-5 60/40 6000 1.4 B-6 40/60 8000 1.4 B-7 30/40/30 8000
1.4 B-8 60/40 8000 1.3 B-9 50/50 6000 1.4 B-10 40/40/20 7000 1.4
B-11 40/30/30 9000 1.6 B-12 30/30/40 6000 1.4 B-13 60/40 9500 1.4
B-14 60/40 8000 1.4 B-15 35/35/30 7000 1.4 B-16 50/40/5/5 6800 1.3
B-17 30/30/50 8000 1.4 B-18 25/25/50 6000 1.4 B-19 100 9500 1.5
B-20 100 7000 1.5 B-21 50/50 6000 1.6 B-22 40/60 9600 1.3 B-23 100
20000 1.7 B-24 100 25000 1.4 B-25 100 15000 1.7 B-26 100 12000 1.8
B-27 100 18000 1.3 B-28 70/30 15000 2.0 B-29 80/15/5 18000 1.8 B-30
60/40 25000 1.8 B-31 90/10 19000 1.6 B-32 60/40 20000 1.8 B-33
50/30/20 11000 1.6 B-34 60/40 12000 1.8 B-35 60/40 15000 1.6 B-36
100 22000 1.8 B-37 20/80 35000 1.6 B-38 30/70 12000 1.7 B-39 30/70
9000 1.5 B-40 100 9000 1.5 B-41 40/15/45 12000 1.9 B-42 30/30/40
13000 2.0 B-43 40/40/20 23000 2.1 B-44 65/30/5 25000 1.6 B-45 100
15000 1.7 B-46 20/80 9000 1.7 B-47 70/30 18000 1.5 B-48 60/20/20
18000 1.8 B-49 100 12000 1.4 B-50 60/40 20000 1.6 B-51 70/30 33000
2.0 B-52 60/40 19000 1.8 B-53 50/50 15000 1.5 B-54 40/20/40 35000
1.9 B-55 100 16000 1.4 (B-1) ##STR00095## (B-2) ##STR00096## (B-3)
##STR00097## (B-4) ##STR00098## (B-5) ##STR00099## (B-6)
##STR00100## (B-7) ##STR00101## (B-8) ##STR00102## (B-9)
##STR00103## (B-10) ##STR00104## (B-11) ##STR00105## (B-12)
##STR00106## (B-13) ##STR00107## (B-14) ##STR00108## (B-15)
##STR00109## (B-16) ##STR00110## (B-17) ##STR00111## (B-18)
##STR00112## (B-19) ##STR00113## (B-20) ##STR00114## (B-21)
##STR00115## (B-22) ##STR00116## (B-23) ##STR00117## (B-24)
##STR00118## (B-25) ##STR00119## (B-26) ##STR00120## (B-27)
##STR00121## (B-28) ##STR00122## (B-29) ##STR00123## (B-30)
##STR00124## (B-31) ##STR00125## (B-32) ##STR00126## (B-33)
##STR00127## (B-34) ##STR00128## (B-35) ##STR00129## (B-36)
##STR00130## (B-37) ##STR00131## (B-38) ##STR00132## (B-39)
##STR00133## (B-40) ##STR00134## (B-41) ##STR00135## (B-42)
##STR00136## (B-43) ##STR00137## (B-44) ##STR00138## (B-45)
##STR00139## (B-46) ##STR00140## (B-47) ##STR00141## (B-48)
##STR00142## (B-49) ##STR00143## (B-50) ##STR00144## (B-51)
##STR00145## (B-52) ##STR00146## (B-53) ##STR00147## (B-54)
##STR00148## (B-55) ##STR00149##
[0455] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention contains a hydrophobic resin
(C) containing at least either a fluorine atom or a silicon atom,
and the resin (C) is unevenly distributed to the surface layer of a
film formed of the actinic-ray-sensitive or radiation-sensitive
resin composition, so that in the case where the liquid for liquid
immersion is water, the receding contact angle for water on the
film surface as well as the traceability of the immersion liquid
can be enhanced.
[0456] The receding contact angle of a film after baking a coating
composed of the actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention of the present invention but
before exposure is preferably from 60 to 90.degree., more
preferably 65.degree. or more, still more preferably 70.degree. or
more, and particularly preferably 75.degree. or more, at the
temperature during exposure (usually room temperature
23.+-.3.degree. C.), and a humidity of 45.+-.5%.
[0457] The resin (C) is, as described above, unevenly distributed
to the interface but unlike a surfactant, need not have necessarily
a hydrophilic group in the molecule and may not contribute to
uniform mixing of polar/nonpolar substances.
[0458] In the liquid immersion exposure step, the liquid for liquid
immersion must move on a wafer following the movement of an
exposure head that is scanning the wafer at a high speed and
forming an exposure pattern. Therefore, the contact angle of the
liquid for liquid immersion with the resist film in a dynamic state
is important, and the resist is required to have a performance of
allowing a liquid droplet to follow the high-speed scanning of an
exposure head with no remaining.
[0459] The resin (C) is hydrophobic and therefore, liable to worsen
the development residue (scum) and BLOB defect after alkali
development, but by virtue of having three or more polymer chains
through at least one branch part, the alkali dissolution rate is
enhanced as compared with a linear chain-type resin and in turn,
the performance in terms of development residue (scum) and the BLOB
defect is improved.
[0460] In the case where the resin (C) contains a fluorine atom,
the fluorine atom content is preferably from 5 to 80% by mass, and
more preferably from 10 to 80% by mass, based on the molecular
weight of the resin (C). Further, the fluorine atom-containing
repeating unit preferably accounts for 10 to 100 mol %, and more
preferably 20 to 100 mol %, based on all the repeating units in the
resin (C).
[0461] In the case where the resin (C) contains a silicon atom, the
silicon atom content is preferably from 2 to 50% by mass, and more
preferably from 2 to 30% by mass, based on the weight average
molecular weight of the resin (C). Further, the silicon
atom-containing repeating unit preferably accounts for 10 to 90 mol
%, and more preferably from 20 to 80 mol %, based on all the
repeating units in the resin (C).
[0462] The weight average molecular weight of the resin (C) is
preferably from 1,000 to 100,000, more preferably from 2,000 to
50,000, and still more preferably from 3,000 to 30,000. Here, the
weight average molecular weight of the resin indicates a molecular
weight in terms of polystyrene measured by GPC (carrier:
tetrahydrofuran (THF)).
[0463] The resin (C) in the actinic-ray-sensitive or
radiation-sensitive resin composition may be used by appropriately
adjusting its content to give an actinic-ray-sensitive or
radiation-sensitive resin film having a receding contact angle in
the range above, but the content thereof is preferably from 0.01 to
20% by mass, more preferably from 0.1 to 15% by mass, still more
preferably from 0.1 to 10% by mass, and particularly preferably
from 0.5 to 8% by mass, based on the total solids of the
actinic-ray-sensitive or radiation-sensitive resin composition.
[0464] The resin (C) may be used singly or in combination of two or
more kinds thereof.
[0465] [4] Basic Compound
[0466] For the purpose of reducing changes in performance with a
lapse of time from exposure to heating, it is preferable that a
basic compound be contained in the actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention.
[0467] Examples of the basic compound include compounds having
structures represented by the following general formulae (A) to
(E).
##STR00150## [0468] In the general formulae (A) and (E), [0469]
R.sup.200, R.sup.201, and R.sup.202 may be the same as or different
from each other, and each of them represents a hydrogen atom, an
alkyl group (preferably having 1 to 20 carbon atoms), and a
cycloalkyl group (preferably having 3 to 20 carbon atoms) or an
aryl group (having 6 to 20 carbon atoms), wherein .sup.201 and
R.sup.202 may be bonded to each other to form a ring, and [0470]
R.sup.203, R.sup.204, R.sup.205, and R.sup.206 may be the same as
or different from each other, and each of them represents an alkyl
group having 1 to 20 carbon atoms.
[0471] As for the alkyl group, the alkyl group having a substituent
is preferably an aminoalkyl group having 1 to 20 carbon atoms, a
hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl
group having 1 to 20 carbon atoms is preferred.
[0472] The alkyl group in any of the general formulae (A) and (E)
is preferably unsubstituted.
[0473] Preferable examples of the compound include guanidine,
aminopyrrolidine, pyrazole, pyrazoline, piperazine,
aminomorpholine, aminoalkyl morpholines, piperidine, and the like;
and these compounds may contain a substituent, and more preferable
examples of such a compound include compounds having an imidazole
structure, a diazabicyclo structure, an onium hydroxide structure,
an onium carboxylate structure, a trialkylamine structure, an
aniline structure, or a pyridine structure; alkylamine derivatives
containing a hydroxyl group and/or an ether bond; aniline
derivatives containing a hydroxyl group and/or an ether bond; and
the like.
[0474] Examples of the compound having an imidazole structure
include imidazole, 2,4,5-triphenylimidazole, benzimidazole,
2-phenylbenzoimidazole, and the like. Examples of the compound
having a diazabicyclo structure include
1,4-diazabicyclo[2,2,2]octane, 1,5-di-azabicyclo[4,3,0]non-5-ene,
1,8-diazabicyclo[5,4,0]undec-7-ene, and the like. Examples of the
compound having an onium hydroxide structure include
triarylsulfonium hydroxides, phenacylsulfonium hydroxides, and
sulfonium hydroxides containing a 2-oxoalkyl group; and specific
examples thereof include triphenylsulfonium hydroxide,
tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium
hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium
hydroxide, and the like. Examples of the compound having an onium
carboxylate structure include compounds in which an anion moiety of
a compound having an onium hydroxide structure is replaced by a
carboxylate, for example, acetate, adamantane-1-carboxylate, a
perfluoroalkyl carboxylate, and the like. Examples of the compound
having a trialkylamine structure include tri(n-butyl)amine,
tri(n-octyl)amine, and the like. Examples of the aniline compound
include 2,6-diisopropylaniline, N,N-dimethylaniline,
N,N-dibutylaniline, N,N-dihexylaniline, and the like. Examples of
the alkylamine derivative containing a hydroxyl group and/or an
ether bond include ethanolamine, diethanolamine, triethanolamine,
N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, and the
like. Examples of the aniline derivative containing a hydroxyl
group and/or an ether bond include N,N-bis(hydroxyethyl)aniline and
the like.
[0475] Preferable examples of the basic compound include an amine
compound having a phenoxy group, an ammonium salt compound having a
phenoxy group, an amine compound having a sulfonic ester group, and
an ammonium salt compound having a sulfonic ester group.
[0476] As the amine compound, a primary, secondary, or tertiary
amine compound can be used, and an amine compound having its at
least one alkyl group bonded to the nitrogen atom thereof is
preferred. Among the amine compounds, a tertiary amine compound is
more preferred. In the amine compounds, as long as at least one
alkyl group (preferably having 1 to 20 carbon atoms) is bonded to
the nitrogen atom, a cycloalkyl group (preferably having 3 to 20
carbon atoms), or an aryl group (preferably having 6 to 12 carbon
atoms) besides the alkyl group may be bonded to the nitrogen atom.
In the amine compounds, it is preferable for the alkyl chain to
contain an oxygen atom so as to form an oxyalkylene group. The
number of oxyalkylene groups in each molecule is 1 or more,
preferably 3 to 9, and more preferably 4 to 6. The oxyalkylene
group is preferably an oxyethylene group (--CH.sub.2CH.sub.2O--) or
an oxypropylene group (--CH(CH.sub.3)CH.sub.2O-- or
--CH.sub.2CH.sub.2CH.sub.2O--), and more preferably an oxyethylene
group.
[0477] As the ammonium salt compound, a primary, secondary,
tertiary, or quaternary ammonium salt compound can be used. An
ammonium salt compound having at least one alkyl group bonded to
the nitrogen atom thereof is preferred. Of the ammonium salt
compounds, as long as at least one alkyl group (preferably having 1
to 20 carbon atoms) is bonded to the nitrogen atom, a cycloalkyl
group (preferably having 3 to 20 carbon atoms) or an aryl group
(preferably having 6 to 12 carbon atoms) besides the alkyl group
may be bonded to the nitrogen atom. Of the ammonium salt compounds,
it is preferable for the alkyl chain to contain an oxygen atom so
as to form an oxyalkylene group. The number of oxyalkylene groups
in each molecule is one or more, preferably 3 to 9, and still more
preferably 4 to 6. The oxyalkylene group is preferably an
oxyethylene group (--CH.sub.2CH.sub.2O--) or an oxypropylene group
(--CH(CH.sub.3)CH.sub.2O-- or --CH.sub.2CH.sub.2CH.sub.2O--), and
more preferably an oxyethylene group.
[0478] Examples of the anion of the ammonium salt compound include
a halide atom, a sulfonate, a borate, a phosphate, and the like,
and among these, a halide and a sulfonate are preferred. As the
halogen atom, chloride, bromide, and iodide are particularly
preferred, and as the sulfonate, an organic sulfonate having 1 to
20 carbon atoms is particularly preferred. Examples of the organic
sulfonate include an aryl sulfonate and an alkyl sulfonate having 1
to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have
a substituent. Examples of the substituent include fluorine,
chlorine, bromine, an alkoxy group, an acyl group, an aryl group,
and the like. Specific examples of the alkyl sulfonate include
methane sulfonate, ethane sulfonate, butane sulfonate, hexane
sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane
sulfonate, pentafluoroethane sulfonate, nonafluorobutane sulfonate,
and the like. Examples of the aryl group of the aryl sulfonate
include a benzene ring, a naphthalene ring, and an anthracene ring.
The benzene ring, the naphthalene ring, or the anthracene ring may
have a substituent. Preferable examples of the substituent include
a linear or branched alkyl group having 1 to 6 carbon atoms and a
cycloalkyl group having 3 to 6 carbon atoms. Specific examples of
the linear or branched alkyl groups and cycloalkyl group include
methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl,
n-hexyl, cyclohexyl, and the like. Examples of such other
substituent include an alkoxy group having 1 to 6 carbon atoms, a
halogen atom, cyano, nitro, an acyl group, an acyloxy group, and
the like.
[0479] The amine compound having a phenoxy group and ammonium salt
compound having a phenoxy group are those having a phenoxy group at
the end of the alkyl group of the amine compound or ammonium salt
compound opposed to the nitrogen atom. The phenoxy group may have a
substituent. Examples of the substituent of the phenoxy group
include an alkyl group, an alkoxy group, a halogen atom, a cyano
group, a nitro group, a carboxyl group, a carboxylic ester group, a
sulfonic ester group, an aryl group, an aralkyl group, an acyloxy
group, an aryloxy group, and the like. The substitution position of
the substituent may be any of 2- to 6-positions. The number of
substituents may be any one within the range of 1 to 5.
[0480] It is preferable that at least one oxyalkylene group exist
between the phenoxy group and the nitrogen atom. The number of
oxyalkylene groups in each molecule is one or more, preferably from
3 to 9, and more preferably from 4 to 6. The oxyalkylene group is
preferably an oxyethylene group (--CH.sub.2CH.sub.2O--) or an
oxypropylene group (--CH(CH.sub.3)CH.sub.2O-- or
--CH.sub.2CH.sub.2CH.sub.2O--), and more preferably an oxyethylene
group.
[0481] The sulfonic ester group of the amine compound having a
sulfonic ester group or ammonium salt compound having a sulfonic
ester group may be any of an alkylsulfonic ester, a
cycloalkylsulfonic ester and an arylsulfonic ester. In the
alkylsulfonic ester, the alkyl group preferably has 1 to 20 carbon
atoms. In the cycloalkylsulfonic ester, the cycloalkyl group
preferably has 3 to 20 carbon atoms. In the arylsulfonic ester, the
aryl group preferably has 6 to 12 carbon atoms. The alkylsulfonic
ester, cycloalkylsulfonic ester and arylsulfonic ester may have
substituents. Preferable examples of the substituent include a
halogen atom, a cyano group, a nitro group, a carboxyl group, a
carboxylic ester group and a sulfonic ester group.
[0482] It is preferable that at least one oxyalkylene group exist
between the sulfonic ester group and the nitrogen atom. The number
of oxyalkylene groups in each molecule is 1 or more, preferably 3
to 9, and more preferably 4 to 6. The oxyalkylene group is
preferably an oxyethylene group (--CH.sub.2CH.sub.2O--) or an
oxypropylene group (--CH(CH.sub.3)CH.sub.2O-- or
--CH.sub.2CH.sub.2CH.sub.2O--), and more preferably an oxyethylene
group.
[0483] Furthermore, the compound is also preferred as a basic
compound.
##STR00151##
[0484] These basic compounds are used singly or in combination of
two or more kinds thereof.
[0485] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention may or may not contain a basic
compound. In the case where the composition contains the basic
compound, the amount of the basic compound to be used is usually
from 0.001 to 10% by mass, and preferably from 0.01 to 5% by mass,
based on the solids of the actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention.
[0486] As for the ratio of the acid generator and the basic
compound to be used in the composition, the acid generator/basic
compound (molar ratio) is preferably 2.5 to 300. That is, the molar
ratio of 2.5 or more is preferred from the viewpoint of sensitivity
and resolution, and 300 or less is preferred from the viewpoint of
inhibition of the reduction of resolution by the thickening of the
pattern in aging after exposure until heat treatment. The ratio of
the acid generator/basic compound (molar ratio) is more preferably
5.0 to 200, and still more preferably 7.0 to 150.
[0487] The basic compound is preferably used with respect to the
(D) low-molecular-weight compound containing a nitrogen atom and
containing a group which is cleaved by the action of an acid, with
a ratio thereof with the (D) low-molecular-weight compound
containing a nitrogen atom and containing a group which is cleaved
by the action of an acid/basic compound (molar ratio)=100/0 to
10/90; preferably a ratio thereof with the (D) low-molecular-weight
compound containing a nitrogen atom and containing a group which is
cleaved by the action of an acid/basic compound (molar ratio)=100/0
to 30/70; and particularly preferably a ratio thereof with the (D)
low-molecular-weight compound containing a nitrogen atom and
containing a group which is cleaved by the action of an acid/basic
compound (molar ratio)=100/0 to 50/50.
[0488] Further, the basic compound as used herein does not include
a (D) low-molecular-weight compound containing a nitrogen atom and
containing a group which is cleaved by the action of an acid, which
is also a basic compound.
[0489] [5] (D) Low-Molecular-Weight Compound Containing Nitrogen
Atom and Containing Group that is Cleaved by Action of Acid
[0490] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention can include a
low-molecular-weight compound containing a nitrogen atom and a
group that is cleaved by the action of an acid (which is also
referred to as a "low-molecular-weight compound (D)" or a "compound
(D)").
[0491] The group that is cleaved by the action of an acid is not
particularly limited, but an acetal group, a carbonate group, a
carbamate group, a tertiary ester group, a tertiary hydroxyl group,
and a hemiaminal ether group are preferred, and a carbamate group
and a hemiaminal ether group are particularly preferred.
[0492] The molecular weight of the low-molecular-weight compound
(D) containing a group that is cleaved by the action of an acid is
preferably 100 to 1000, more preferably 100 to 700, and
particularly preferably 100 to 500.
[0493] As the compound (D), an amine derivative containing group
that is cleaved by the action of an acid on a nitrogen atoms is
preferred.
[0494] The compound (D) may contain a carbamate group having a
protecting group on a nitrogen atom. The protecting group
constituting the carbamate group can be represented by the
following general formula (d-1).
##STR00152## [0495] In the general formula (d-1), [0496] each Rb
independently represents a hydrogen atom, an alkyl group, a
cycloalkyl group, an aryl group, an aralkyl group, or an
alkoxyalkyl group, and Rb's may be bonded to each other to form a
ring.
[0497] The alkyl group, the cycloalkyl group, the aryl group, or
the aralkyl group represented by Rb may be substituted with a
functional group such as a hydroxyl group, a cyano group, an amino
group, a pyrrolidino group, a piperidino group, a morpholino group,
an oxo group, and the like, an alkoxy group, or a halogen atom.
This case comes under the alkoxyalkyl group represented by Rb.
[0498] Examples of the alkyl group, the cycloalkyl group, the aryl
group, or the aralkyl group of Rb above (the alkyl group, the
cycloalkyl group, the aryl group, and the aralkyl group may be
substituted with the above-described functional group, an alkoxy
group, or a halogen atom) include: [0499] a group derived from a
linear or branched alkane such as methane, ethane, propane, butane,
pentane, hexane, heptane, octane, nonane, decane, undecane,
dodecane, and the like, or a group where the group derived from an
alkane is substituted with one or more kinds of or one or more
groups of cycloalkyl groups such as a cyclobutyl group, a
cyclopentyl group, a cyclohexyl group, and the like; [0500] a group
derived from a cycloalkane such as cyclobutane, cyclopentane,
cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane,
noradamantane, and the like, or a group where the group derived
from a cycloalkane is substituted with one or more kinds of or one
or more groups of linear or branched alkyl group such as a methyl
group, an ethyl group, an n-propyl group, an i-propyl group, an
n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a
t-butyl group, and the like; [0501] a group derived from an
aromatic compound such as benzene, naphthalene, anthracene, and the
like, or a group where the group derived from an aromatic compound
is substituted with one or more kinds of or one or more groups of
linear or branched alkyl group such as a methyl group, an ethyl
group, an n-propyl group, an i-propyl group, an n-butyl group, a
2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, and
the like; [0502] a group derived from a heterocyclic compound such
as pyrrolidine, piperidine, morpholine, tetrahydrofuran,
tetrahydropyran, indole, indoline, quinoline, perhydroquinoline,
indazole, benzimidazole, and the like, or a group where the group
derived from a heterocyclic compound is substituted with one or
more kinds of or one or more groups of linear or branched alkyl
group or aromatic compound-derived group; [0503] a group where the
group derived from a linear or branched alkane or the group derived
from a cycloalkane is substituted with one or more kinds of or one
or more groups of aromatic compound-derived group such as a phenyl
group, a naphthyl group, an anthracenyl group, and the like; [0504]
a group where the substituent above is substituted with a
functional group such as a hydroxyl group, a cyano group, an amino
group, a pyrrolidino group, a piperidino group, a morpholino group,
an oxo group, and the like; etc.
[0505] Rb is preferably a linear or branched alkyl group, a
cycloalkyl group, or an aryl group, and more preferably a linear or
branched alkyl group or a cycloalkyl group.
[0506] Examples of the ring formed by the mutual bonding of two
Rb's include an alicyclic hydrocarbon group, an aromatic
hydrocarbon group, a heterocyclic hydrocarbon group, and
derivatives thereof.
[0507] Specific structures of the group represented by the general
formula (d-1) will be shown below.
##STR00153## ##STR00154## ##STR00155##
[0508] The compound (D) can be formed by any combination of the
basic compound and a structure represented by the general formula
(d-1).
[0509] The compound (D) is particularly preferably one having a
structure represented by the following general formula (A).
[0510] Further, the compound (D) may correspond to the basic
compound as long as it is a low-molecular-weight compound
containing group which is cleaved by the action of an acid.
##STR00156##
[0511] In the general formula (A), Ra represents a hydrogen atom,
an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl
group. Further, with n=2, two Ra's may be the same as or different
from each other, or the two Ra's may be bonded to each other to
form a divalent heterocyclic hydrocarbon group (preferably having
20 or less carbon atoms) or a derivative thereof.
[0512] Rb has the same meaning as Rb in the general formula (d-1),
and preferable examples thereof are also the same. However, in
--C(Rb)(Rb)(Rb), when one or more Rb's are hydrogen atoms, at least
one of the remaining Rb's is a cyclopropyl group, a 1-alkoxyalkyl
group, or an aryl group.
[0513] n represents an integer of 0 to 2, and m represents an
integer of 1 to 3, with n+m=3.
[0514] In the general formula (A), the alkyl group, the cycloalkyl
group, the aryl group, or the aralkyl group represented by Ra may
be the same substituent as one which substitutes the alkyl group,
the cycloalkyl group, the aryl group, or the aralkyl group
represented by Rb.
[0515] Specific examples of the alkyl group, the cycloalkyl group,
the aryl group, or the aralkyl group of Ra (the alkyl group, the
cycloalkyl group, the aryl group, or the aralkyl group may be
substituted with the above-described group) are the same as those
described with respect to Rb.
[0516] Furthermore, examples of the divalent heterocyclic
hydrocarbon group (preferably having 1 to 20 carbon atoms) formed
by the mutual bonding of Ra's or a derivative thereof include a
group derived from a heterocyclic compound, such as pyrrolidine,
piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine,
1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine,
homopiperazine, 4-azabenzimidazole, benzotriazole,
5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane,
tetrazole, 7-azaindole, indazole, benzimidazole,
imidazo[1,2-a]pyridine, (1S,4S)-(+)-2,5-diazabicyclo[2.2.1]heptane,
1,5,7-triazabicyclo[4.4.0]dec-5-ene, indole, indoline,
1,2,3,4-tetrahydroquinoxaline, perhydroquinoline,
1,5,9-triazacyclododecane, and the like; a group as obtained by
substituting the above heterocyclic-compound-derived group with at
least one or at least one type of linear or branched-alkane-derived
group, cycloalkane-derived group, aromatic-compound-derived group,
heterocyclic-compound-derived group or functional group, such as a
hydroxyl group, a cyano group, an amino group, a pyrrolidino group,
a piperidino group, a morpholino group, an oxo group, and the like;
etc.
[0517] Specific particularly preferable examples of the compound
(D) will be shown below, but the present invention is not limited
thereto.
##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161##
##STR00162## ##STR00163## ##STR00164## ##STR00165##
##STR00166##
[0518] The compound represented by the general formula (A) can be
synthesized according to JP2007-298569A, JP2009-199021A, or the
like.
[0519] In the present invention, the low-molecular-weight compound
(D) containing a nitrogen atom and containing a group that is
cleaved by the action of an acid may be used singly or used after
mixing two or more kinds thereof.
[0520] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention may not include the
low-molecular-weight compound (D) containing a nitrogen atom and
containing a group that is cleaved by the action of an acid, but if
included, the content of the compound (D) is usually from 0.001 to
20% by mass, preferably from 0.001 to 10% by mass, and more
preferably from 0.01 to 5% by mass, based on all the solids of the
composition combined with the basic compound.
[0521] With respect to the ratio of the acid generator to the
compound (D) to be used in the resin composition, the acid
generator/[compound (D)+the basic compound] (molar ratio) is
preferably 2.5 to 300. The reason for this is that the molar ratio
is preferred to be 2.5 or more from the viewpoint of sensitivity
and resolving power. The molar ratio is preferred to be 300 or less
from the viewpoint of the inhibition of any resolving power
deterioration due to thickening of resist pattern over time from
exposure to heating treatment. The acid generator/[the compound
(D)+the basic compound] (molar ratio) is more preferably from 5.0
to 200, and still more preferably from 7.0 to 150.
[0522] [6] Solvent
[0523] Examples of a solvent which can be used in dissolving the
foregoing respective components therein to prepare the
actinic-ray-sensitive or radiation-sensitive resin composition
include an alkylene glycol monoalkyl ether carboxylate, an alkylene
glycol monoalkyl ether, a lactic acid alkyl ether, an alkyl
alkoxypropionate, a cyclic lactone (having 4 to 10 carbon atoms), a
monoketone compound which may contain a ring (having 4 to 10 carbon
atoms), an alkylene carbonate, an alkyl alkoxyacetate, an alkyl
pyruvate, and the like.
[0524] Preferable examples of the alkylene glycol monoalkyl ether
carboxylate include propylene glycol monomethyl ether acetate,
propylene glycol monoethyl ether acetate, propylene glycol
monopropyl ether acetate, propylene glycol monobutyl ether acetate,
propylene glycol monomethyl etherpropionate, propylene glycol
monoethyl etherpropionate, ethylene glycol monomethyl ether
acetate, and ethylene glycol monoethyl ether acetate.
[0525] Preferable examples of the alkylene glycol monoalkyl ether
include propylene glycol monomethyl ether, propylene glycol
monoethyl ether, propylene glycol monopropyl ether, propylene
glycol monobutyl ether, ethylene glycol monomethyl ether, and
ethylene glycol monoethyl ether.
[0526] Preferable examples of the lactic acid alkyl ester include
methyl lactate, ethyl lactate, propyl lactate, and butyl
lactate.
[0527] Preferable examples of the alkyl alkoxypropionate include
ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl
3-ethoxypropionate, and ethyl 3-methoxypropionate.
[0528] Preferable examples of the cyclic lactone include
.beta.-propiolactone, .beta.-butyrolactone, .gamma.-butyrolactone,
.alpha.-methyl-.gamma.-butyrolactone,
.beta.-methyl-.gamma.-butyrolactone, .gamma.-valerolactone,
.gamma.-caprolactone, .gamma.-octanoic lactone, and
.alpha.-hydroxy-.gamma.-butyrolatone.
[0529] Preferable examples of the ketone compound which may contain
a ring include 2-butanone, 3-methylbutanone, pinacolone,
2-pentanone, 3-pentanone, 3-methyl-2-pentanone,
4-methyl-2-pentanone, 2-methyl-3-pentanone,
4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone,
2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone,
5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone,
2-methyl-3-heptanone, 5-methyl-3-heptanone,
2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone,
3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone,
5-hexecen-2-one, 3-penten-2-one, cyclopentanone,
2-methylcyclopentanone, 3-methyl cyclopentanone,
2,2-dimethyl-cyclopentanone, 2,4,4-trimethylcyclopentanone,
cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone,
4-ethylcyclohexanone, 2,2-dimethylcyclohexanone,
2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone,
cycloheptanone, 2-methylcycloheptanone, and
3-methylcycloheptanone.
[0530] Preferable examples of the alkylene carbonate include
propylene carbonate, vinylene carbonate, ethylene carbonate, and
butylene carbonate.
[0531] Preferable examples of the alkyl alkoxyacetate include
2-methoxyethyl acetate, 2-ethoxyethyl acetate,
2-(2-ethoxyethoxy)ethyl acetate, 3-methoxy-3-methylbutyl acetate,
and 1-methoxy-2-propyl acetate.
[0532] Preferable examples of the alkyl pyruvate include methyl
pyruvate, ethyl pyruvate, and propyl pyruvate.
[0533] Examples of the solvent which can be preferably used include
solvents having a boiling point of 130.degree. C. or higher at the
ordinary temperature under an atmospheric pressure. Specific
examples thereof include cyclopentanone, .gamma.-butyrolactone,
cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether
acetate, propylene glycol monomethyl ether acetate, ethyl
3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate,
2-(2-ethoxyethoxy)ethyl acetate, and propylene carbonate.
[0534] In the present invention, these solvents may be used singly
or in combination of two or more kinds thereof.
[0535] In the present invention, a mixed solvent of a solvent
containing a hydroxyl group in a structure thereof and a hydroxyl
group-free solvent may be used as the organic solvent.
[0536] Examples of the hydroxyl group-containing solvent include
ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol
monoethyl ether, propylene glycol, propylene glycol monomethyl
ether, propylene glycol monoethyl ether, ethyl lactate, and the
like, with propylene glycol monomethyl ether and ethyl lactate
being more preferred. Further, as the hydroxyl group-free solvent,
alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, a
monoketone compound which may contain a ring, cyclic lactone, alkyl
acetate, and the like are preferred, and among these, propylene
glycol monomethyl ether acetate, ethyl ethoxy propionate,
2-heptanone, .gamma.-butyrolactone, cyclohexanone and butyl acetate
are particularly preferred, and propylene glycol monomethyl ether
acetate, ethylethoxypropionate, and 2-heptanone are most
preferred.
[0537] A mixing ratio (by weight) of the hydroxyl group-containing
solvent to the hydroxyl group-free solvent is from 1/99 to 99/1,
preferably from 10/90 to 90/10, and more preferably from 20/80 to
60/40. A mixed solvent containing 50% by weight or more of the
hydroxyl group-free solvent is particularly preferable in view of
coating uniformity.
[0538] The solvent is preferably a mixture of two or more kinds of
solvents, including propylene glycol monomethyl ether acetate.
[0539] [7] Surfactant
[0540] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention may or may not further contain
a surfactant. If the composition contains the surfactant, it is
preferable that the composition contain any one, or two or more
members, of fluorinated and/or siliconized surfactants (fluorinated
surfactant, siliconized surfactant and surfactant containing both
fluorine and silicon atoms).
[0541] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention when containing the above
surfactant would, in the use of an exposure light source of 250 nm
or less, and particularly 220 nm or less, realize favorable
sensitivity and resolving power and produce a resist pattern with
less adhesion and development defects.
[0542] Examples of the fluorinated and/or siliconized surfactant
include those described in in the specification of U.S. Patent
Application Publication No. 2008/0248425. Any of the following
commercially available surfactants can be used as is. Examples of
the useful commercially available surfactant include fluorinated
surfactants/siliconized surfactants, such as Eftop EF301 and EF303
(available from Shin-Akita Kasei Co., Ltd.), Fluorad FC 430, 431
and 4430 (available from Sumitomo 3M Limited.), Megafac F171, F173,
F176, F189, F113, F110, F177, F120, and R08 (available from
Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102,
103, 104, 105, and 106 (available from Asahi Glass Co., Ltd.),
Troysol S-366 (available from Troy Chemical Co., Ltd.), GF-300 and
GF-150 (available from Toagosei Co., Ltd.), Surflon S-393
(available from Seimi Chemical Co., Ltd.), Eftop EF121, EF122A,
EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, and
EF601 (available from JEMCO Inc.), PF636, PF656, PF6320, and PF6520
(available from OMNOVA Solutions Inc.), FTX-204G; 208G, 218G, 230G,
204D, 208D, 212D, 218D, and 222D (available from NEOS), and the
like. Further, a polysiloxane polymer KP-341 (available from
Shin-Etsu Chemical Co., Ltd.) can be employed as the siliconized
surfactant.
[0543] As the surfactant, besides the publicly known surfactants as
shown above, a surfactant based on a polymer having a fluorinated
aliphatic group derived from a fluorinated aliphatic compound,
produced by a telomerization technique (also called a telomer
process) or an oligomerization technique (also called an oligomer
process) can be used. The fluorinated aliphatic compound can be
synthesized by the method described in JP2002-90991A.
[0544] The polymer having a fluorinated aliphatic group is
preferably a copolymer from a monomer having a fluorinated
aliphatic group and a poly(oxyalkylene)acrylate and/or
poly(oxyalkylene)methacrylate, which copolymer may have an
irregular distribution or may result from block copolymerization.
Examples of the poly(oxyalkylene) group include a poly(oxyethylene)
group, a poly(oxypropylene) group, a poly(oxybutylene) group, and
the like. Further, a unit having alkylene groups of different chain
lengths in a single chain, such as poly(oxyethylene-oxypropyl
ene-oxyethylene block concatenation) and
poly(oxyethylene-oxypropylene block concatenation) may be used.
Moreover, the copolymer from a monomer having a fluorinated
aliphatic group and a poly(oxyalkylene) acrylate (or methacrylate)
is not limited to two-monomer copolymers and may be a three or more
monomer copolymer obtained by simultaneous copolymerization of two
or more different monomers having a fluorinated aliphatic group,
two or more different poly(oxyalkylene)acrylates (or
methacrylates), and the like.
[0545] Examples thereof include, as a commercially available
surfactant, Megafac F178, F-470, F-473, F-475, F-476, and F-472
(available from Dainippon Ink & Chemicals, Inc.), and further a
copolymer from an acrylate (or methacrylate) having a
C.sub.6F.sub.13 group and a poly(oxyalkylene)acrylate (or
methacrylate), a copolymer from an acrylate (or methacrylate)
having a C.sub.3F.sub.7 group, poly(oxyethylene)acrylate (or
methacrylate) and poly(oxypropylene)acrylate (or methacrylate), and
the like.
[0546] Furthermore, in the present invention, a surfactant other
than the fluorinated and/or siliconized surfactant described in
[0280] in the specification of U.S. Patent Application Publication
No. 2008/0248425, may also be used.
[0547] These surfactants may be used singly or in combination of
two or more kinds thereof.
[0548] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention may or may not contain a
surfactant, but in the case where the composition contains a
surfactant, the content of the surfactant is preferably from 0 to
2% by mass, still more preferably from 0.0001 to 2% by mass, and
particularly preferably from 0.0005 to 1% by mass, based on the
total solids (total amount excluding the solvent) of the
actinic-ray-sensitive or radiation-sensitive resin composition.
[0549] On the other hand, it is preferable to set the amount of the
surfactant to be added to 10 ppm or less. By this, the hydrophobic
resin is more unevenly distributed to the surface, so that the
resist film surface can be made more hydrophobic and the
traceability of water at the liquid immersion exposure can be
enhanced.
[0550] [8] Onium Carboxylate
[0551] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention may contain an onium
carboxylate. The onium carboxylate is preferably an iodonium salt
or a sulfonium salt. The anion moiety is preferably a linear,
branched, monocyclic, or polycyclic alkylcarboxylate anion having 1
to 30 carbon atoms, more preferably the carboxylate anion above
with the alkyl group being partially or entirely
fluorine-substituted. The alkyl chain may contain an oxygen atom.
Thanks to such a configuration, the transparency to light at 220 nm
or less is ensured, the sensitivity and resolution are enhanced,
and the iso/dense bias and exposure margin are improved.
[0552] Examples of the fluorine-substituted carboxylate anion
include anions of fluoroacetate, difluoroacetate, trifluoroacetate,
pentafluoropropionate, heptafluorobutyrate, nonafluoropentanoate,
perfluorododecanoate, perfluorotridecanoate,
perfluorocyclohexanecarboxylate, 2,2-bistrifluoromethylpropionate,
and the like.
[0553] The content of the onium carboxylate in the composition is
generally from 0.1 to 20% by mass, preferably from 0.5 to 10% by
mass, and more preferably from 1 to 7% by mass, based on the total
solids of the composition.
[0554] [9] Dissolution-Suppressing Compound Having Molecular Weight
of 3000 or Less, Which Decomposes by Action of Acid to Increase
Solubility in Alkaline Developer
[0555] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention may contain a
dissolution-suppressing compound having a molecular weight of 3000
or less, which decomposes by the action of an acid to increase a
solubility in an alkaline developer (which is also referred to as a
"dissolution-suppressing compound"). Since the
dissolution-suppressing compound does not suppress the penetration
at 220 nm or less, it is preferably an alicyclic or aliphatic
compound containing an acid-decomposable group, such as
acid-decomposable group-containing cholic acid derivative described
in Proceeding of SPIE, 2724, 355 (1996), so as not to reduce the
transmittance at 220 nm or less. Examples of the acid-decomposable
group and alicyclic structure are the same as those described above
with respect to the resin (A).
[0556] In the case where the actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention is
exposed to KrF excimer laser or irradiated with an electron beam,
the dissolution-suppressing compound preferably has a structure
where a phenolic hydroxyl group of a phenol compound is substituted
with an acid-decomposable group. The phenol compound is preferably
a compound containing from 1 to 9 phenol skeleton, and more
preferably from 2 to 6 phenol skeleton.
[0557] The amount of the dissolution-suppressing compound added is
preferably from 3 to 50% by mass, and more preferably from 5 to 40%
by mass, based on the total solids of the actinic-ray-sensitive or
radiation-sensitive resin composition.
[0558] Specific examples of the dissolution-suppressing compound
are shown below, but the present invention is not limited
thereto.
##STR00167##
[0559] [10] Other Additives
[0560] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention may further contain, for
example, a dye, a plasticizer, a photosensitizer, a light absorber,
a compound for accelerating dissolution in a developer (for
example, a phenol compound having a molecular weight of 1000 or
less, or a carboxyl group-containing alicyclic or aliphatic
compound), or the like, if desired. Further, it is ensured that the
content of the solids in the composition of the present invention
(based on the solids) is no more than 100% by mass in total.
[0561] The phenol compound having a molecular weight of 1000 or
less can be easily synthesized by one skilled in the art by
referring to the method described, for example, in JP4-122938A,
JP2-28531A, U.S. Pat. No. 4,916,210, European Patent 219294, and
the like.
[0562] Specific examples of the carboxyl group-containing alicyclic
or aliphatic compound include, but are not limited to, a carboxylic
acid derivative having a steroid structure, such as cholic acid,
deoxycholic acid, lithocholic acid, and the like, an
adamantanecarboxylic acid derivative, an adamantanedicarboxylic
acid, a cyclohexanecarboxylic acid, a cyclohexanedicarboxylic acid,
and the like.
<Pattern Forming Method>
[0563] The pattern forming method of the present invention includes
steps of exposing and developing the resist film.
[0564] The resist film is formed from the above-described
actinic-ray-sensitive or radiation-sensitive resin composition of
the present invention, and more specifically, it is preferably
formed on a substrate. The pattern forming method of the present
invention can be carried out by a generally known method, including
forming a film from the resist composition on a substrate, exposing
the film, and developing the film.
[0565] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention is preferably used in a film
thickness of 30 to 250 nm, and more preferably from 30 to 200 nm,
from the viewpoint of enhancing the resolving power. Such a film
thickness can be obtained by setting the solid concentration in the
actinic-ray-sensitive or radiation-sensitive resin composition to
an appropriate range, thereby imparting an appropriate viscosity
and enhancing the coatability and the film-forming property.
[0566] The total solid concentration in the actinic-ray-sensitive
or radiation-sensitive resin composition is generally from 1 to 10%
by mass, preferably from 1 to 8.0% by mass, and more preferably
from 1.0 to 6.0% by mass.
[0567] The actinic-ray-sensitive or radiation-sensitive resin
composition of the present invention is used by dissolving the
components above in a predetermined organic solvent, preferably in
the above-described solvent mixture, filtering the solution, and
coating it on a predetermined support as follows. The filter used
for filtration is preferably a polytetrafluoroethylene-,
polyethylene-, or nylon-made filter having a pore size of 0.1 .mu.m
or less, more preferably 0.05 .mu.m or less, and still more
preferably 0.03 .mu.m or less. Further, two or more kinds of the
filters can be connected serially or in parallel, and then used.
Further, the composition may be filtered two or more times.
Further, before and after the filtration with a filter, the
composition may be subjected to a deaeration treatment, or the
like.
[0568] For example, the actinic-ray-sensitive or
radiation-sensitive resin composition can be applied onto a
substrate, such as one for use in the production of integrated
circuit elements (for example, silicon/silicon dioxide coating), by
appropriate application means, such as a spinner, a coater, and the
like, and dried to obtain a resist film.
[0569] This resist film is irradiated with an actinic-ray or a
radiation through a predetermined mask, preferably baked (heated),
developed, and rinsed. Thus, a favorable pattern can be
obtained.
[0570] After preparing the film and before the exposure step, a
prebake process (PB; Prebake) is also preferably included.
[0571] In addition, after the exposure step and before the
development step, a heating step (PEB; Post Exposure Bake) is also
preferably included.
[0572] As for the heating temperature, heating of any of PB and PEB
is preferably at a temperature of 70 to 120.degree. C., and more
preferably at a temperature of 80 to 110.degree. C.
[0573] The heat time is preferably 30 to 300 seconds, more
preferably 30 to 180 seconds, and still more preferably 30 to 90
seconds.
[0574] Heating may be carried out by a unit included in an
exposure/development apparatus, and may also be carried out using a
hot plate or the like.
[0575] By the baking, the reaction of the exposed portion is
accelerated and the sensitivity or pattern profile is improved.
[0576] Examples of the actinic-ray or the radiation include
infrared rays, visible light, ultraviolet rays, far ultraviolet
rays, X-rays, an electron beam, and the like. Far ultraviolet rays
having a wavelength of preferably 250 nm or shorter, more
preferably 220 nm or shorter, and particularly preferably 1 to 200
nm, specifically, for example, a KrF excimer laser (248 nm), an ArF
excimer laser (193 nm), an F.sub.2 excimer laser (157 nm), X-rays,
EUV (13 nm), an electron beam, and the like are preferred, and an
ArF excimer laser, a F.sub.2 excimer laser, EUV (13 nm), and an
electron beam are more preferred.
[0577] Prior to the formation of a resist film, an antireflection
film may also be coated.
[0578] As the antireflection film, not only an inorganic film of
titanium, titanium oxide, titanium nitride, chromium oxide, carbon,
amorphous silicon and the like but also an organic film composed of
a light absorber and a polymer substance can be used. Further, as
the organic antireflection film, commercially available organic
antireflection films, such as the DUV30 Series and DUV40 Series
available from Brewer Science Inc., AR-2, AR-3, and AR-5 available
from Shipley Co., L.L.C., and the like can also be used.
[0579] As the alkaline developer in the development step, a
quaternary ammonium salt, typically such as tetramethylammonium
hydroxide is used, but an inorganic alkali, a primary amine, a
secondary amine, a tertiary amine, an alcoholamine, a cycloamine,
and the like can also be used.
[0580] In addition, to the above alkaline developer, appropriate
amounts of an alcohol and a surfactant may be further added.
[0581] The alkali concentration of the alkaline developer is
generally from 0.1 to 20% by mass.
[0582] The pH value of the alkaline developer is generally from
10.0 to 15.0.
[0583] Further, an alcohol or a surfactant can be added to the
aqueous basic solution, and the mixture can be used.
[0584] Pure water can be used as the rinse liquid, and an
appropriate amount of a surfactant may be added thereto and then
used.
[0585] As the development method, use can be made of, for example,
a method in which the substrate is dipped in a tank filled with a
developer for a given period of time (dip method), a method in
which a developer is mounded on the surface of the substrate by its
surface tension and allowed to stand still for a given period of
time to thereby effect development (puddle method), a method in
which a developer is sprayed onto the surface of the substrate
(spray method), a method in which a developer is continuously
applied onto the substrate rotating at a given speed while scanning
a developer application nozzle at a given speed (dynamic dispense
method), or the like.
[0586] Furthermore, the developer or rinsing liquid attached on a
pattern after the development step or rinsing step can be subjected
to a removal treatment by a supercritical fluid.
[0587] The film formed using the actinic-ray-sensitive or
radiation-sensitive resin composition of the present invention may
be subjected to liquid immersion exposure. That is, the interstice
between the film and a lens may be filled with a liquid whose
refractive index is higher than that of air during irradiation with
an actinic-ray or a radiation. This would bring about an
enhancement of the resolution.
[0588] A liquid for liquid immersion which is used in the liquid
immersion exposure will be described below.
[0589] As the liquid for liquid immersion, a liquid which is
transparent to the exposure wavelength and which has a temperature
coefficient of refractive index as small as possible for the
purpose of controlling a strain of an optical image to be projected
on the actinic-ray-sensitive or radiation-sensitive film in the
minimum level is preferred. In particular, when the exposure light
source is ArF excimer laser (wavelength: 193 nm), water is
preferably used in view of easy availability and easy handling in
addition to the foregoing viewpoints.
[0590] Moreover, a medium having a refractive index of 1.5 or more
may also be used in view of attaining a shorter wavelength. This
medium may be either an aqueous solution or an organic solvent.
[0591] When water is used as the liquid for liquid immersion, for
the purposes of not only reducing a surface tension of water but
also increasing a surface-active power, an additive (liquid) which
does not dissolve the resist layer on a wafer and whose influences
against an optical coat on a lower face of a lens element can be
neglected may be added in a little proportion.
[0592] As such an additive, an aliphatic alcohol having a
refractive index substantially equal to water is preferable.
Specific examples thereof include methyl alcohol, ethyl alcohol,
isopropyl alcohol, and the like. By adding an alcohol having a
refractive index substantially equal to water, even when the
alcohol component in water is evaporated, whereby the concentration
of the alcohol changes, an advantage such that the change in
refractive index as the whole liquid can be made extremely small.
On the other hand, when a substance opaque to the 193-nm light or
an impurity having a refractive index largely different from water
is incorporated, a strain of an optical image to be projected on
the actinic-ray-sensitive or radiation-sensitive film is generated.
Accordingly, the water to be used is preferably distilled water.
Further, pure water obtainable by carrying out filtration of the
distilled water through an ion exchanging filter may also be
used.
[0593] With the water to be used as a liquid for liquid immersion,
the electrical resistance is preferably 18.3 M.OMEGA.cm or more,
and the TOC (total organic carbon) is preferably 20 ppb or less.
Further, the water has been preferably subjected to a deaeration
treatment.
[0594] Furthermore, by increasing the refractive index of the
liquid for liquid immersion, it is possible to enhance a
lithography performance. From such viewpoints, an additive capable
of increasing a refractive index may be added to the water, or
heavy water (D.sub.2O) may be used in place of the water.
[0595] In order that the resist film may not come into direct
contact with the liquid for liquid immersion, a layer which is
sparingly soluble in the liquid for liquid immersion (hereinafter
referred to as "top coat") may be provided between the resist film
(photosensitive layer) according to the positive composition of the
invention and the liquid for liquid immersion. Examples of the
function necessary as a top coat include coating aptitude for a
resist film, transparence against a radioactive ray, especially a
radioactive ray at 193 nm, and sparing solubility in the liquid for
liquid immersion. It is preferable that the top coat does not mix
with the resist film and is able to be uniformly coated on the
resist film.
[0596] With respect to the top coat, from the viewpoint of
transparency against a radioactive ray at 193 nm, an aromatic
ring-free polymer is preferable. Examples thereof include a
hydrocarbon polymer, an acrylic ester polymer, a polymethacrylic
acid, a polyacrylic acid, a polyvinyl ether, a silicon-containing
polymer, and a fluorine-containing polymer. The above-described
hydrophobic resin is also suitable as a top coat. From the
viewpoint that when an impurity elutes from the top coat into the
liquid for liquid immersion, it stains an optical lens, it is
preferable that the amount of residual monomer components of the
polymer contained in the top coat is small.
[0597] In stripping the top coat, the developer may be used, or a
stripper may be separately used. As the stripper, a solvent having
low penetration into the resist film is preferable. In view of the
matter that the stripping step can be carried out simultaneously
with the developing treatment step of the resist, it is preferable
that stripping can be achieved by the alkaline developer. From the
viewpoint that stripping is achieved by the alkaline developer, it
is preferable that the top coat is acidic. However, from the
viewpoint of non-intermixing properties with the resist, the top
coat may also be neutral or basic.
[0598] The difference in refractive index between the top coat and
the liquid for liquid immersion is preferably small or none, which
brings about improvement of the resolving power. In the case where
the exposure light source is ArF excimer laser (wavelength: 193
nm), water is preferably used as the liquid for liquid immersion.
As a result, it is preferable that the top coat for ArF immersion
exposure have a refractive index closed to that of water (1.44). In
addition, the top coat is preferably a thin layer from the
viewpoints of transparency and a refractive index.
[0599] Moreover, it is preferable that the top coat does not mix
with the resist film and does not mix with the liquid for liquid
immersion. Further, from this viewpoint, in the case where the
liquid for liquid immersion is water, it is preferable that a
solvent of the top coat is a medium which is sparingly soluble in
the solvent used in the actinic-ray-sensitive or
radiation-sensitive composition and insoluble in water. In
addition, when the liquid for liquid immersion is an organic
solvent, the top coat may be soluble in water or may be insoluble
in water.
[0600] As the alkaline developer in the development step, a
quaternary ammonium salt, typically such as tetramethylammonium
hydroxide is used, but an inorganic alkali, a primary amine, a
secondary amine, a tertiary amine, an alcoholamine, a cycloamine,
and the like can also be used. To the alkaline developer,
appropriate amounts of an alcohol and a surfactant may also be
added.
[0601] The alkali concentration of the alkaline developer is
generally from 0.1 to 20% by mass.
[0602] The pH value of the alkaline developer is generally from
10.0 to 15.0.
[0603] Pure water can be used as the rinse liquid, and an
appropriate amount of a surfactant may be added thereto and then
used. Further, the developer or rinsing liquid attached on a
pattern after the development treatment or rinsing treatment may
also be subjected to a removal treatment by a supercritical
fluid.
EXAMPLES
[0604] The present invention will be explained below in more detail
by reference to Examples, but the present invention is not limited
thereto.
[0605] The repeating units in the resin (A) used in Examples will
be shown below.
##STR00168## ##STR00169## ##STR00170##
[0606] The repeating units in the resin used in Comparative
Examples will be shown below.
##STR00171## ##STR00172##
Synthesis Example 1
Synthesis of Resin (A)
Synthesis of Resin (A-1)
[0607] Under a nitrogen air flow, 40 g of cyclohexanone was put
into a three-neck flask, and heated at 80.degree. C. (Solvent 1).
The monomers corresponding to the respective repeating units were
dissolved in cyclohexanone at a molar ratio of 40/10/50 to prepare
a solution of 22% by mass of the monomer (400 g). Further, 7.2 mol
% of a polymerization initiator (V-601, available from Wako Pure
Chemical Industries, Ltd.) based on the monomer was added thereto
and dissolved. The prepared solution was added dropwise to the
Solvent 1 over 6 hours. After addition dropwise, the obtained
solution was further subjected to a reaction at 80.degree. C. for 2
hours. The obtained reaction liquid was left to be cooled, and then
poured into 3600 ml of heptane/400 ml of ethyl acetate. The
precipitated solid (powder) was collected by filtration, and dried
to obtain 74 g of a resin (A-1). The polymer compositional ratio
determined by NMR was 40/10/50 (molar ratio). Further, the weight
average molecular weight and the dispersity (Mw/Mn) of the obtained
resin (A-1) were 10200 and 1.53, respectively.
[0608] The same procedure as in Synthesis Example 1 was carried out
to synthesize the resins (A-2) to (A-17) and (AA-1) to (AA-6).
[0609] Regarding the resins (A-1) to (A-17) and (AA-1) to (AA-6),
the repeating units, the compositional ratios (molar ratios), the
weight average molecular weights, and the dispersities are shown in
Tables 2 and 3. The compositional ratios sequentially correspond to
the respective repeating units from the left side.
TABLE-US-00002 TABLE 2 Synthesis Compositional Molecular Example LM
IM PM ratio weight Dispersity A-1 LM-1 IM-1 PM-1 -- 40/10/50 10200
1.53 A-2 LM-1 IM-1 PM-1 PM-3 40/10/35/15 9500 1.54 A-3 LM-1 IM-1
PM-2 -- 40/10/50 8400 1.52 A-4 LM-1 IM-1 PM-3 -- 40/10/50 10000
1.49 A-5 LM-1 IM-1 PM-4 -- 40/10/50 9200 1.56 A-6 LM-1 IM-1 PM-5 --
40/10/50 10500 1.51 A-7 LM-1 IM-1 PM-1 -- 50/10/40 9300 1.53 A-8
LM-1 IM-1 PM-1 -- 30/10/60 8700 1.60 A-9 LM-1 IM-1 PM-1 -- 55/5/40
10300 1.52 A-10 LM-1 IM-1 PM-5 -- 50/10/40 9200 1.55 A-11 LM-1 IM-1
PM-1 PM-3 40/10/25/25 9000 1.53 A-12 LM-1 -- PM-1 -- 40/60 9700
1.56 A-13 LM-1 -- PM-2 -- 40/60 10100 1.57 A-14 LM-1 -- PM-1 PM-3
50/25/25 9400 1.54 A-15 LM-1 -- PM-1 PM-5 40/40/20 9600 1.53 A-16
LM-1 IM-1 PM-1 PM-9 40/10/35/15 9700 1.53 A-17 LM-4 IM-2 PM-10 --
40/10/50 9900 1.54
TABLE-US-00003 TABLE 3 Composi- Synthesis tional Molecular Disper-
Example NM IM PM ratio weight sity AA-1 LM-2 IM-1 PM-1 -- 40/10/50
8900 1.57 AA-2 LM-3 IM-1 PM-1 40/10/50 9200 1.56 AA-3 LM-1 IM-1
PM-6 -- 40/10/50 9500 1.52 AA-4 LM-1 IM-1 PM-7 -- 40/10/50 8800
1.54 AA-5 LM-1 IM-1 PM-8 -- 40/10/50 9300 1.56 AA-6 LM-1 IM-1 PM-9
-- 40/10/50 9000 1.54
Synthesis Example 2
Synthesis of Hydrophobic Resin r1
[0610] The monomers corresponding to the following repeating units
were dissolved in propylene glycol monomethyl ether acetate (PGMEA)
each at a ratio of 50/50 (molar ratio) to prepare 450 g of a
solution having a solid concentration of 15% by mass. To this
solution was added 1 mol % of a polymerization initiator (V-60,
available from Wako Pure Chemical Industries, Ltd.) and added
dropwise to 50 g of PGMEA that had been heated at 100.degree. C.
over 6 hours under nitrogen atmosphere. After dropwise addition,
the reaction liquid was stirred for 2 hours. After completion of
the reaction, the reaction liquid was cooled to room temperature,
and crystallized with 5 L of methanol. The precipitated white
powder was collected by filtration to recover a hydrophobic resin
r1 as a desired product.
[0611] The polymer compositional ratio determined by NMR was 50/50.
Further, the weight average molecular weight and the dispersity
were 4000 and 1.4, respectively, as measured by GPC in terms of a
polystyrene standard.
[0612] In the same manner as in Synthesis Example 2 except that the
monomers corresponding to the respective repeating units were used
at the predetermined compositional ratios (molar ratios),
hydrophobic resins r2 to r8 were synthesized.
[0613] The structures of the hydrophobic resins r1 to r8 are shown
below. Further, the compositional ratios (molar ratios), the weight
average molecular weights, and the dispersities of the hydrophobic
resins r1 to r8 are shown in Table 4.
TABLE-US-00004 TABLE 4 Compositional ratio Resin (molar ratio) Mw
Dispersity r1 50/50 4000 1.4 r2 50/50 5500 1.6 r3 50/50 6500 1.6 r4
90/8/2 13000 1.5 r5 39/57/2/2 4200 1.4 r6 40/40/15/5 4800 1.5 r7
20/80 6000 1.4 r8 50/50 5200 1.5 r1 ##STR00173## r2 ##STR00174## r3
##STR00175## r4 ##STR00176## r5 ##STR00177## r6 ##STR00178## r7
##STR00179## r8 ##STR00180##
Synthesis Example 3
Synthesis of Compound (b39)
[0614] In accordance with [0316] of JP2004-139014A, as the compound
represented by the general formula (ZI-3), the compound (b39)
described above was synthesized.
[0615] Similarly, as the compound represented by the general
formula (ZI-3), the compounds (b11), (b13), (b21), (b31), (b36) to
(b39), (b41), (b43), and (b45) to (b50) described above, and the
acid generators (J1), (J3), (J7), and (J8) represented by the
following formulae were synthesized.
##STR00181##
[0616] The abbreviations in Tables 5 and 6 are as follows.
[0617] The compounds (b11), (b13), (b21), (b31), (b36) to (b39),
(b41), (b43), (b45) to (b50), (J1), (J3), (J7), and (J8) are as
shown above.
[0618] N-1: 2,6-Diisopropylaniline [0619] N-2:
Tetrabutylammoniumhydroxide [0620] N-3:
Tris(methoxyethoxyethyl)amine [0621] N-4: N-Phenyldiethanolamine
[0622] N-5: Trioctylamine [0623] N-6: 2-Phenylbenzoimidazole [0624]
N-7: N,N-Dihexylaniline [0625] N-8: Triethanolamine [0626] N-9:
N,N-Dibutylaniline [0627] C-13 and C-58 are as shown above.
[0628] AD-1 to AD-3: Each of them represents the following
compound.
##STR00182##
[0629] W-1: PolyFox.TM. PF-6320 (available from OMNOVA Solutions
Inc.) (fluorinated) [0630] W-2: Troysol S-336 (available from Troy
Chemical Co., Ltd.) [0631] W-3: Polysiloxane polymer KP-341
(available from Shin-Etsu Chemical Co., Ltd) (siliconized)
[0632] SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
[0633] SL-2: Cyclohexanone [0634] SL-3: Propylene glycol monomethyl
ether (PGME) [0635] SL-4: .gamma.-Butyrolactone [0636] SL-5:
Propylene carbonate
[0637] [Preparation of Actinic-Ray-Sensitive or Radiation-Sensitive
Resin Composition]
[0638] The components shown in Tables 5 and 6 below were dissolved
in a solvent to prepare each of the resist solutions, and the
solutions were filtered through a polyethylene filter having a pore
size of 0.03 .mu.m to prepare an actinic-ray-sensitive or
radiation-sensitive resin composition. The prepared
actinic-ray-sensitive or radiation-sensitive resin composition was
evaluated by the following method, and the results are shown in the
Table.
[0639] [Image Performance Test]
[0640] ARC29SR for forming an organic antireflection film
(available from Nissan Chemical Industries, Ltd.) was coated on a
silicon wafer and baked at 205.degree. C. for 60 seconds to form an
antireflection film having a film thickness of 86 nm. The
actinic-ray-sensitive or radiation-sensitive resin composition
prepared above was coated thereon and baked at 100.degree. C. for
60 seconds to form a resist film having a film thickness of 90 nm.
The obtained wafer was subjected to exposure through a 6% halftone
mask with a line width of 48 nm and a pattern of line:space=1:1,
using an ArF excimer laser liquid immersion scanner (available from
ASML, XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma
0.895, XY deflection). Ultrapure water was used as the liquid for
liquid immersion. Thereafter, the resist film was heated at
105.degree. C. for 60 seconds, then developed with an aqueous
tetramethylammonium hydroxide solution (2.38% by mass) for 30
seconds, rinsed with pure water, and then spin-dried to obtain a
resist pattern.
[0641] The compositions of Examples 1 to 29 and Comparative
Examples 1 to 8 shown in Table 5 were subjected to patterning by
liquid immersion exposure as described above and evaluated, and the
results are shown in Table 5.
[0642] Further, in the column of "Addition Configuration" in Table
5, the addition configuration of the hydrophobic resin is described
as "Added" or "TC". In the examples in which "Added" is described,
the hydrophobic resin is included in the resist solution. In the
examples in which "TC" is described, a resist film is formed using
a resist solution including no hydrophobic resin, and then a top
coat (TC) protective film including a hydrophobic resin is formed
on the upper layer.
[0643] In the case where the addition configuration of the
hydrophobic resin is "TC", after the resist film was formed, the
following procedure was carried out. In addition, the solvents
mentioned in the column of the "Solvent in the case of TC" are as
follows.
[0644] SL-6: 2-Ethylbutanol [0645] SL-7:
Perfluorobutyltetrahydrofuran
[0646] <Method for Forming Top Coat>
[0647] The hydrophobic resin was dissolved in a solvent, and the
obtained solution was coated on the resist film using a spin
coater. Thereafter, this was heated and dried at 115.degree. C. for
60 seconds to form a top coat layer having a film thickness of 0.05
.mu.m. After forming the top coat layer, the coating deviation of
the top coat layer was observed, and it was thus confirmed that the
top coat layer was coated uniformly.
[0648] Furthermore, regarding the compositions of Examples 30 to 33
and Comparative Examples 9 and 10 show in Table 6, evaluation was
carried out in the same manner as for patterning by liquid
immersion exposure above except that a liquid for liquid immersion
was not used and a 1:1 line-and-space pattern having a line width
of 75 nm was formed by dry exposure (ArF excimer laser scanner, NA
0.75). The results are shown in Table 6.
[0649] [Method for Evaluating Critical Dimension Uniformity (CDU)
in Line Width]
[0650] At an exposure amount when the line width with a 1:1
line-and-space pattern was 48 nm in the liquid immersion exposure
and 75 nm in the dry exposure respectively, 100 values of line
width (CD) amount the respective line patterns were measured, and a
value of three times (3.sigma.) of the standard deviation (.sigma.)
of an average value calculated from the measured results were
determined to evaluate the critical dimension uniformity (CDU) of
the CD. The results in the case of the liquid immersion exposure
and the results in the case of the dry exposure are shown in Tables
5 and 6, respectively. For the 3.sigma. determined as above, a
smaller value of the 3.sigma. indicates a higher critical dimension
uniformity (CDU) of each line CD formed in the resist film.
TABLE-US-00005 TABLE 5 Composition Acid Basic Surfac- generator
compound or Additive tant Hydrophobic Addition Resin A (parts
compound (parts (parts resin configu- (parts by (D) (parts by by by
(parts by ration Solvent in Solvent (parts Test results by mass)
mass) mass) mass) mass) mass) (Added/TC) case of TC by mass) CDU
(nm) Ex. 1 A-1 b38 N-1 W-1 r1 Added SL-1/SL-3 5.3 (90.48) (7.1)
(0.42) (0.50) (1.0) (1140/760) Ex. 2 A-2 b39 N-6 W-1 r1 TC SL-6
SL-1/SL-3 5.5 (76.78) (20.6) (1.12) (0.50) (1.0) (1140/760) Ex. 3
A-10 b41 N-2 W-2 r2 Added SL-1 (1900) 5.2 (83.30) (14.4) (0.80)
(0.50) (1.0) Ex. 4 A-14 b36 N-2 AD-1 W-3 r3 Added SL-1/SL-2/SL-3
5.1 (80.19) (16.7) (1.11) (0.5) (0.50) (1.0) (1641/244/15) Ex. 5
A-1 b49 N-5 AD-1 W-1 r4 Added SL-1/SL-3/SL-4 5.3 (74.74) (20.2)
(1.06) (0.5) (0.50) (3.0) (1438/442/20) Ex. 6 A-4 b45 N-9 W-3 r3
Added SL-1 (1900) 5.2 (83.05) (14.5) (0.95) (0.50) (1.0) Ex. 7 A-3
b46 N-1 AD-2 W-1 r5 Added SL-1/SL-2/SL-5 5.6 (78.05) (18.0) (1.45)
(0.7) (0.50) (1.0) (1354/531/15) Ex. 8 A-1 b47 N-2 W-1 r2 Added
SL-1/SL-3 5.4 (82.51) (15.0) (0.99) (0.50) (1.0) (1140/760) Ex. 9
A-7 b49 N-8 AD-2 W-2 r6 Added SL-1/SL-3 5.1 (75.26) (21.1) (1.44)
(0.7) (0.50) (1.0) (1140/760) Ex. 10 A-8 b48 N-7 W-3 r1 Added
SL-1/SL-3 5.3 (83.75) (14.0) (0.75) (0.50) (1.0) (1140/760) Ex. 11
A-3 b49 N-2 W-1 r5 Added SL-1/SL-3 5.4 (82.14) (15.8) (0.56) (0.50)
(1.0) (1140/760) Ex. 12 A-2 b50 N-4 AD-1 W-1 r5 TC SL-7 SL-1/SL-3
5.6 (77.99) (19.1) (0.91) (0.5) (0.50) (1.0) (1140/760) Ex. 13 A-6
b38/J7 N-4 W-2 r4 Added SL-1 (1900) 5.2 (82.89) (7.0/6.1) (0.51)
(0.50) (3.0) Ex. 14 A-1 b49 N-3 W-3 r1 Added SL-1/SL-2/SL-3 5.3
(82.05) (15.5) (0.95) (0.50) (1.0) (1641/244/15) Ex. 15 A-11 b46
N-5 AD-1 W-1 r5 Added SL-1/SL-3/SL-4 5.5 (78.49) (18.3) (1.21)
(0.5) (0.50) (1.0) (1438/442/20) Ex. 16 A-12 b39/J1 N-3 AD-1 W-1 r7
Added SL-1/SL-3 5.4 (80.64) (10.0/6.4) (0.96) (0.5) (0.50) (1.0)
(1140/760) Ex. 17 A-1 b45 N-9 W-1 r4/r5 Added SL-1/SL-3 5.3 (77.42)
(18.6) (1.18) (0.50) (2.0/0.3) (1140/760) Ex. 18 A-9 b45 N-1 r1
Added SL-1 (1900) 5.2 (82.75) (15.2) (1.05) (1.0) Ex. 19 A-3 b49/J7
N-4 W-1 r5 Added SL-1/SL-3 5.4 (75.00) (18.0/3.9) (1.60) (0.50)
(1.0) (1140/760) Ex. 20 A-1 b50 N-1 r5 Added SL-1/SL-3 5.5 (81.85)
(16.2) (0.95) (1.0) (1140/760) Ex. 21 A-2 b41 N-8 W-1 r1 TC SL-6
SL-1/SL-3 5.6 (87.60) (10.2) (0.70) (0.50) (1.0) (1140/760) Ex. 22
A-5 b47 N-3 AD-1 W-2 r5 Added SL-1 (1900) 5.4 (83.03) (14.5) (0.47)
(0.5) (0.50) (1.0) Ex. 23 A-15 b36 C-13 W-1 r4 Added SL-1 (1900)
5.3 (71.28) (24.7) (0.52) (0.50) (3.0) Ex. 24 A-13 b38 C-58 AD-1
W-1 r5 Added SL-1 (1900) 5.2 (85.38) (12.3) (0.32) (0.5) (0.50)
(1.0) Ex. 25 A-16 b11/J1 N-3 W-1 r4/r5 Added SL-1/SL-3 5.5 (75.70)
(12.0/8.5) (1.00) (0.50) (2.0/0.3) (1140/760) Ex. 26 A-1 b13 C-13
AD-1 r8 Added SL-1 (1900) 5.5 (74.88) (22.4) (1.22) (0.5) (1.0) Ex.
27 A-17 b21 N-1 W-1 r4 Added SL-1/SL-3 5.6 (78.71) (16.9) (0.89)
(0.50) (3.0) (1140/760) Ex. 28 A-1/A-3 b45 N-4 AD-1 W-1 r5 Added
SL-1 (1900) 5.3 (35.15/35.15) (26.2) (1.50) (0.5) (0.50) (1.0) Ex.
29 .sup. A-1/AA-1 b49 N-2 r1 Added SL-1/SL-3 5.4 (38.90/38.90)
(20.1) (1.11) (1.0) (1140/760) Comp. AA-1 b31 N-9 W-1 r1 TC SL-7
SL-1/SL-3 6.5 Ex. 1 (92.28) (6.1) (0.12) (0.50) (1.0) (1140/760)
Comp. AA-2 b36 N-5 AD-1 W-1 r4 Added SL-1/SL-3 6.5 Ex. 2 (87.78)
(7.9) (0.32) (0.5) (0.50) (3.0) (1140/760) Comp. AA-3 b37 N-3 W-1
r3 Added SL-1/SL-3 6.4 Ex. 3 (89.11) (9.1) (0.29) (0.50) (1.0)
(1140/760) Comp. AA-4 b38 N-2 AD-1 W-1 r1 Added SL-1/SL-3 6.4 Ex. 4
(85.69) (11.1) (1.21) (0.5) (0.50) (1.0) (1140/760) Comp. AA-5 b39
N-1 AD-1 W-3 r1 Added SL-1/SL-3 6.3 Ex. 5 (87.20) (10.0) (0.8)
(0.5) (0.50) (1.0) (1140/760) Comp. AA-6 b47 C-58 W-1 r4 Added
SL-1/SL-3 6.1 Ex. 6 (79.96) (15.5) (1.04) (0.50) (3.0) (1140/760)
Comp. A-1 J8 N-2 W-1 r1 Added SL-1/SL-3 6.2 Ex. 7 (86.88) (10.4)
(1.22) (0.50) (1.0) (1140/760) Comp. A-1 J1 N-1 W-3 r1 Added
SL-1/SL-3 6.3 Ex. 8 (92.10) (6.0) (0.40) (0.50) (1.0)
(1140/760)
[0651] As clearly shown from Table 5, it can be seen that any of
Comparative Examples 1 and 2 in which the resins having no
repeating unit represented by the general formula (A-I) were used,
Comparative Examples 3 to 6 in which the resins having no repeating
unit represented by the general formula (1) were used, and
Comparative Examples 7 and 8 in which the acid generators other
than the compound represented by the general formula (ZI-3) were
used, showed poor results with high CDU.
[0652] With this regard, it can be seen that Examples 1 to 29 in
which the resins having both of the repeating unit represented by
the general formula (A-I) and the repeating unit represented by the
general formula (1), and the compound represented by the general
formula (ZI-3) were used, showed excellent results with low CDU in
the liquid immersion exposure.
TABLE-US-00006 TABLE 6 Composition Acid Basic Resin A generator
compound or Additive Surfactant Test (parts by (parts by compound
(D) (parts by (parts by Solvent results mass) mass) (parts by mass)
mass) mass) (parts by mass) CDU (nm) Ex. 30 A-1 b49 (8.1) N-3
(0.43) W-1 (0.50) SL-1/SL-3 4.3 (90.97) (1140/760) Ex. 31 A-2 b46
(22.8) N-5 (1.33) SL-1/SL-3 3.8 (75.87) (1140/760) Ex. 32 A-5 b39
(13.4) N-1 (0.75) W-2 (0.50) SL-1 (1900) 4.4 (85.35) Ex. 33 A-12
b48 (17.6) N-9 (1.44) AD-3 (0.5) W-3 (0.50) SL-1/SL-2/SL-3 3.9
(79.96) (1641/244/15) Comp. AA-6 b43 (13.6) N-5 (0.80) W-1 (0.50)
SL-1/SL-3 5.2 Ex. 9 (85.10) (1140/760) Comp. A-4 J3 (7.4) N-1
(0.25) W-1 (0.50) SL-1/SL-3 5.1 Ex. 10 (91.85) (1140/760)
[0653] As clearly shown from Table 6, it can be seen that any of
Comparative Example 9 in which a resin having no repeating unit
represented by the general formula (1) was used and Comparative
Example 10 in which an acid generator other than the compound
represented by the general formula (ZI-3) was used, showed poor
results with high CDU.
[0654] With this regard, it can be seen that Examples 30 to 33 in
which resins having both of the repeating unit represented by the
general formula (A-I) and the repeating unit represented by the
general formula (1) and the compound represented by the general
formula (ZI-3) were used, showed excellent results in the liquid
immersion exposure with low CDU.
* * * * *